WO2018143382A1 - Binder agent composition for lithium battery - Google Patents

Binder agent composition for lithium battery Download PDF

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Publication number
WO2018143382A1
WO2018143382A1 PCT/JP2018/003513 JP2018003513W WO2018143382A1 WO 2018143382 A1 WO2018143382 A1 WO 2018143382A1 JP 2018003513 W JP2018003513 W JP 2018003513W WO 2018143382 A1 WO2018143382 A1 WO 2018143382A1
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Prior art keywords
group
carbon atoms
general formula
integer
alkylene group
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PCT/JP2018/003513
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French (fr)
Japanese (ja)
Inventor
水田　浩徳
一樹 瀧本
博美 綿引
歌穂 杉本
隆敏 松浦
訓明 岡本
信孝 嶋村
Original Assignee
富士フイルム和光純薬株式会社
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Application filed by 富士フイルム和光純薬株式会社 filed Critical 富士フイルム和光純薬株式会社
Priority to JP2018566104A priority Critical patent/JP7041399B2/en
Priority to EP18747843.3A priority patent/EP3579313B1/en
Priority to KR1020197014353A priority patent/KR102548023B1/en
Priority to CN201880004294.1A priority patent/CN109923711B/en
Priority to US16/482,973 priority patent/US11258066B2/en
Publication of WO2018143382A1 publication Critical patent/WO2018143382A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a binder composition, a slurry composition and an electrode used in a lithium battery, and a method for producing the electrode.
  • Lithium batteries are used as power sources for various portable devices such as mobile phones as secondary batteries, but in recent years, research and development of large batteries that are intended for automobile applications and the like have become active. Therefore, it has become indispensable to further increase the energy density of current lithium batteries.
  • a silicon material instead of a carbon-based material as an active material.
  • silicon can cause an alloying reaction with lithium electrochemically at room temperature, resulting in a higher electric capacity than when carbon is used. It is thought to be caused.
  • silicon when silicon is used as an active material, it is known that silicon undergoes a large volume change (enlarged to 3 times or more) during charge and discharge. This volume change has a problem that the electrode structure is destroyed during charge / discharge, resulting in a decrease in charge / discharge capacity.
  • Patent Documents 1 and 2 various attempts have been made to use a binder for the purpose of increasing the capacity of the battery and improving the stability performance.
  • these target active materials are mainly carbon materials, and are not intended to solve the above problems when silicon is used.
  • an attempt has been made to suppress a decrease in charge / discharge capacity by coating a silicon active material with a thermosetting resin (Patent Document 3).
  • the coating requires a heat treatment at 400 ° C., silicon It was not a method that can easily produce an electrode using the active material.
  • An object of the present invention is to provide an excellent binder composition that solves the above problems, a slurry composition and an electrode using the same, and a method for producing the electrode.
  • the present inventors have studied various binders in order to solve the above problem when silicon is used as an active material. As a result, when an active material containing silicon is used by using, as a binder, a composition comprising a polymer, a divalent to 10-valent alcohol for bonding the polymers, and water. In addition, the present inventors have found that an excellent charge / discharge capacity can be obtained and completed the present invention.
  • the present invention includes the following inventions [i] to [xiii].
  • a binder composition comprising (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water. (Hereinafter, it may be abbreviated as the binder composition of the present invention.)
  • the composition according to the above-mentioned invention [i], wherein the divalent to 10-valent alcohol of (B) is a compound represented by the following general formula (B1); Wherein R 71 represents an alkylene group having 1 to 6 carbon atoms, R 72 represents a hydroxy group or a hydroxyalkyl group having 1 to 6 carbon atoms, R 73 represents a hydrogen atom, 1 to 6 carbon atoms Or an alkyl group having 1 to 6 carbon atoms, R 74 represents an alkylene group having 1 to 6 carbon atoms which may have —O— in the chain, and r represents 0 to 4 carbon atoms.
  • [Iii] (A) comprises polyacrylic acid and a monomer unit derived from acrylic acid and one or two monomer units derived from a compound represented by the following general formula (I) or general formula (II)
  • V represents an integer of 2 to 20); or a group represented by the following general formula (V) (Wherein R 5 to R 7 each independently represents an alkyl group having 1 to 3 carbon atoms, and R 8 represents an alkylene group having 1 to 3 carbon atoms).
  • R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms
  • R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms
  • d represents an integer of 1 to 6
  • e represents an integer of 0 to 6
  • f and g Each independently represents an integer of 0 or 1.
  • R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group).
  • R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms
  • ring Ar 1 represents a benzene ring or a naphthalene ring
  • R 49 represents an alkylene group having 1 to 6 carbon atoms
  • h represents an integer of 2 to 4
  • each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring
  • R 50 represents an alkylene group having 1 to 6 carbon atoms).
  • R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1] (Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5).
  • R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2] (Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3] (Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000.
  • [V] The above invention, wherein the polyacrylic acid and / or copolymer is crosslinked with a crosslinking agent selected from the compounds represented by the following general formulas [1] to [13] and the polymer represented by the following general formula [14]:
  • [Iii] a composition according to the description; (Wherein, a represents an integer of 1 to 6), [Wherein R 25 and R 26 each independently represent a hydrogen atom or a methyl group, R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1] (Wherein R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6), or a group represented by the following general formula [2-2] (Wherein R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22).
  • R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms
  • R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms
  • d represents an integer of 1 to 6
  • e represents an integer of 0 to 6
  • f and g Each independently represents an integer of 0 or 1.
  • R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group).
  • R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms
  • ring Ar 1 represents a benzene ring or a naphthalene ring
  • R 49 represents an alkylene group having 1 to 6 carbon atoms
  • h represents an integer of 2 to 4
  • each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring
  • R 50 represents an alkylene group having 1 to 6 carbon atoms).
  • R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1] (Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5).
  • R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2] (Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3] (Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000.
  • the active material containing silicon contains silicon, silicon oxide, silicon bonded to metal, or a mixture of carbon, silicon, silicon oxide, or silicon bonded to metal, at least two kinds A composition according to the invention [vii].
  • Active material containing silicon includes silicon, silicon oxide, silicon bonded to metal, or a mixture of at least two of carbon, silicon, silicon oxide, or silicon bonded to metal
  • a lithium electrode using the binder composition of the present invention, it is possible to provide an electrode that maintains a high charge / discharge capacity even when an active material containing silicon is used. Further, by using the electrode, it is possible to provide a battery that can maintain a high capacity for a long period of time.
  • the binder solution is a term indicating an aqueous solution in which one or more kinds of polymers and other compounds (additives such as a crosslinking agent) are mixed with water, and the binder refers to the binder solution. It is a term that indicates a state in which moisture has been removed by drying.
  • the binder composition of the present invention is a kind of binder solution, and the binder derived from the binder composition of the present invention is a kind of binder.
  • (meth) acrylic acid is a generic term for acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.
  • n- represents normal-form and i- represents iso-form.
  • the binder composition of the present invention contains at least polyacrylic acid and, if necessary, a polymer other than polyacrylic acid.
  • (A) one or more kinds of polymers containing polyacrylic acid means (A1) only polyacrylic acid, or (A2) a polymer composed of a polymer other than polyacrylic acid and one or more kinds of polyacrylic acid. Means group.
  • the polymer other than the polyacrylic acid may be a conventionally known polymer that is usually used in this field, and may be a homopolymer or a copolymer.
  • the polymer other than polyacrylic acid may be one type or two or more types, and only one type is preferable.
  • a polymer including a monomer unit having a carboxy group as a constituent component is preferable, a copolymer including a monomer unit having a carboxy group as a constituent component is more preferable, and a copolymer including a monomer unit derived from acrylic acid as a constituent component Is more preferable.
  • copolymer containing a monomer unit derived from acrylic acid as a constituent component include, for example, a monomer unit derived from acrylic acid and a monomer unit 1 derived from a compound represented by the following general formula (I) or general formula (II).
  • Copolymers having two or more components as constituents hereinafter sometimes abbreviated as copolymers according to the present invention can be mentioned.
  • the alkyl group having 1 to 20 carbon atoms in R 2 of the general formula (I) preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable.
  • alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom in R 2 of the general formula (I) those having a terminal portion fluorinated are preferred, and a perfluoroalkyl group or a (perfluoroalkyl) alkyl group is Preferably, a (perfluoroalkyl) alkyl group is more preferable. Further, those having 1 to 10 carbon atoms are preferable, and a straight chain is preferable.
  • alkyl group having 1 to 20 carbon atoms substituted with a hydroxy group in R 2 of the general formula (I) those having a terminal portion substituted with a hydroxy group are preferable, and 1 to 2 hydrogen atoms are substituted with a hydroxy group. Those in which one hydrogen is replaced with a hydroxy group are more preferable. Further, those having 1 to 6 carbon atoms are preferred, and a straight chain is preferred.
  • Examples include hydroxyoctadecyl group, hydroxynonadecyl group, hydroxyicosyl group, etc., among which hydroxymethyl group, hydroxyethyl group, dihydroxyethyl , Hydroxypropyl group
  • Examples of the aryl group having 6 to 10 carbon atoms in R 2 of the general formula (I) include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • the arylalkyl group having 7 to 13 carbon atoms in R 2 of the general formula (I) is preferably one having 7 to 9 carbon atoms.
  • Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, etc.
  • a benzyl group, a phenylethyl group, and a phenylpropyl group are preferable, and a benzyl group is preferable. More preferred.
  • Examples of the alkoxyalkyl group having 2 to 9 carbon atoms in R 2 of the general formula (I) include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, methoxyhexyl group, methoxyheptyl group, methoxy Octyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, ethoxypentyl group, ethoxyhexyl group, ethoxyheptyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, propoxybutyl group, propoxypentyl group And propoxyhexyl group.
  • Examples of the alkoxyalkoxyalkyl group having 3 to 9 carbon atoms in R 2 of the general formula (I) include a methoxymethoxymethyl group, a methoxymethoxyethyl group, a methoxymethoxypropyl group, an ethoxymethoxymethyl group, an ethoxymethoxyethyl group, and an ethoxymethoxypropyl group.
  • the aryloxyalkyl group having 7 to 13 carbon atoms in R 2 of the general formula (I) is preferably one having 7 to 9 carbon atoms.
  • Specific examples include a phenoxymethyl group, a phenoxyethyl group, a phenoxypropyl group, a naphthyloxymethyl group, a naphthyloxyethyl group, a naphthyloxypropyl group, and the like, among which a phenoxymethyl group, a phenoxyethyl group, and a phenoxypropyl group are mentioned.
  • a phenoxyethyl group is more preferable.
  • Examples of the morpholinoalkyl group having 5 to 7 carbon atoms in R 2 of the general formula (I) include a morpholinomethyl group, a morpholinoethyl group, a morpholinopropyl group, and the like.
  • Examples of the trialkylsilyl group having 3 to 9 carbon atoms in R 2 of the general formula (I) include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group and the like.
  • Examples of the alicyclic hydrocarbon group having 6 to 12 carbon atoms having an oxygen atom in R 2 of the general formula (I) include a dicyclopentenyloxyethyl group.
  • Examples of the alicyclic hydrocarbon group having 6 to 12 carbon atoms and having no oxygen atom in R 2 of the general formula (I) include a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.
  • dialkylaminoalkyl group having 3 to 9 carbon atoms in R 2 of the general formula (I) examples include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, A propylaminomethyl group, a dipropylaminoethyl group, a dipropylaminopropyl group, etc. are mentioned.
  • the alkyl group of the hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms in R 2 of the general formula (I) usually has 1 to 6 carbon atoms, preferably one having 1 to 3 carbon atoms, Those are preferred.
  • Specific examples of the hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms include 2-hexahydrophthalimidomethyl group, 2-hexahydrophthalimidoethyl group, 2-hexahydrophthalimidopropyl group, and 2-hexahydrophthalimido group. Examples thereof include hydrophthalimidobutyl group, 2-hexahydrophthalimidopentyl group, and 2-hexahydrophthalimidohexyl group.
  • alkylene group having 1 to 6 carbon atoms having a hydroxy group as a substituent in R 3 of the general formula (IV) one in which one hydrogen is substituted with a hydroxy group is preferable, and one having 1 to 3 carbon atoms is preferred.
  • Specific examples include a hydroxymethylene group, a hydroxyethylene group, a hydroxytrimethylene group, a hydroxytetramethylene group, a hydroxypentamethylene group, and a hydroxyhexamethylene group.
  • a hydroxymethylene group, a hydroxyethylene group, a hydroxytrimethylene group, and the like can be given. Group is preferred, and hydroxytrimethylene group is more preferred.
  • the unsubstituted alkylene group having 1 to 6 carbon atoms in R 3 of the general formula (IV) is preferably one having 2 to 4 carbon atoms.
  • Specific examples include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., among which an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group are preferable, An ethylene group and a propylene group are more preferable, and an ethylene group is particularly preferable.
  • the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV) preferably has 1 to 3 carbon atoms.
  • any of linear, branched, and cyclic may be sufficient, and linear is preferable.
  • R 3 in the general formula (IV) is preferably an unsubstituted alkylene group having 2 to 6 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 4 carbon atoms, among which an ethylene group, a trimethylene group, a propylene group, A tetramethylene group is preferable, an ethylene group and a propylene group are more preferable, and an ethylene group is particularly preferable.
  • R 4 in the general formula (IV) is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.
  • v is preferably an integer of 2 to 10, and more preferably an integer of 4 to 10.
  • the v — (R 3 —O) — groups may be the same or different.
  • Specific examples of the group represented by the general formula (IV) include polyethylene glycol group, methyl polyethylene glycol group, ethyl polyethylene glycol group, n-propyl polyethylene glycol group, isopropyl polyethylene glycol group, phenyl polyethylene glycol group, polytrimethylene glycol.
  • polypropylene glycol group methyl polypropylene glycol group, ethyl polypropylene glycol group, n-propyl polypropylene glycol group, isopropyl polypropylene glycol group, phenyl polypropylene glycol group, polytetramethylene glycol group, polypentamethylene glycol group, polyhexamethylene glycol group
  • Examples of the alkyl group having 1 to 3 carbon atoms in R 5 to R 7 in the general formula (V) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable.
  • Examples of the alkylene group having 1 to 3 carbon atoms in R 8 of the general formula (V) include a methylene group, an ethylene group, and a trimethylene group.
  • Specific examples of the group represented by the general formula (V) include trimethyl ammonium methyl group, trimethyl ammonium ethyl group, trimethyl ammonium propyl group, triethyl ammonium methyl group, triethyl ammonium ethyl group, triethyl ammonium propyl group and the like.
  • R 1 in the general formula (I) may be a hydrogen atom or a methyl group, but when R 2 is a hydrogen atom, it represents a methyl group.
  • R 2 in the general formula (I) is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an arylalkyl group having 7 to 13 carbon atoms.
  • R 101 represents a hydrogen atom or a methyl group (provided that when R 102 is a hydrogen atom, R 101 represents a methyl group), R 102 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms] An alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an arylalkyl group having 7 to 13 carbon atoms; an aryloxyalkyl group having 7 to 13 carbon atoms; hexahydrophthalimide having 9 to 14 carbon atoms; An N-alkyl group; or a group represented by the following general formula (IV-I) (Wherein R 103 represents an unsubstituted alkylene group having 2 to 6 carbon atoms, R 104 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and v is the
  • the unsubstituted alkylene group having 2 to 6 carbon atoms in R 103 of the general formula (IV-I) is preferably one having 2 to 4 carbon atoms.
  • ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like can be mentioned, among which ethylene group, trimethylene group, propylene group and tetramethylene group are preferable, ethylene group, A propylene group is more preferable, and an ethylene group is particularly preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 104 of the general formula (IV-I) include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). It is.
  • R 104 in formula (IV-I) is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • Specific examples of the group represented by the general formula (IV-I) include polyethylene glycol group, methyl polyethylene glycol group, ethyl polyethylene glycol group, n-propyl polyethylene glycol group, isopropyl polyethylene glycol group, polytrimethylene glycol group, polypropylene.
  • Examples include glycol group, methyl polypropylene glycol group, ethyl polypropylene glycol group, n-propyl polypropylene glycol group, isopropyl polypropylene glycol group, polytetramethylene glycol group, polypentamethylene glycol group, polyhexamethylene glycol group, polyethylene glycol group Methyl polyethylene glycol group, polypropylene glycol group and methyl polypropylene glycol group are preferred.
  • Lumpur group more preferably a methyl polyethylene glycol group.
  • R 101 in the general formula (II) may be either a hydrogen atom or a methyl group, but when R 102 is a hydrogen atom, it represents a methyl group.
  • R 102 in the general formula (II) is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; aryloxyalkyl having 7 to 13 carbon atoms Or a group represented by formula (IV-I) is preferred, a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group is more preferred, and the number of carbon atoms substituted with a hydroxy group Particularly preferred are 1 to 20 alkyl groups.
  • More preferred specific examples of the compound represented by the general formula (I) include compounds represented by the following general formula (I-II).
  • R 201 represents a hydrogen atom or a methyl group (provided that when R 202 is a hydrogen atom, R 201 represents a methyl group), R 202 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms]
  • R 203 represents an unsubstituted alkylene group having 2 to 4 carbon atoms
  • R 204 represents a hydrogen atom
  • An alkyl group having 1 to 20 carbon atoms in R 202 of formula (I-II); an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; and an aryloxyalkyl group having 7 to 13 carbon atoms are the same as those in R 2 of the general formula (I), and preferable ones are also the same.
  • Examples of the unsubstituted alkylene group having 2 to 4 carbon atoms in R 203 of the general formula (IV-II) include an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group. Among them, an ethylene group and a propylene group are preferable. An ethylene group is more preferable.
  • Examples of the alkyl group having 1 to 3 carbon atoms in R204 of the general formula (IV-II) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable.
  • R 204 in formula (IV-II) is preferably a hydrogen atom or a methyl group.
  • Specific examples of the group represented by the general formula (IV-II) include polyethylene glycol group, methyl polyethylene glycol group, ethyl polyethylene glycol group, n-propyl polyethylene glycol group, isopropyl polyethylene glycol group, polytrimethylene glycol group, polypropylene.
  • Examples include glycol group, methyl polypropylene glycol group, ethyl polypropylene glycol group, n-propyl polypropylene glycol group, isopropyl polypropylene glycol group, polytetramethylene glycol group, polyethylene glycol group, methyl polyethylene glycol group, polypropylene glycol group, methyl polypropylene glycol.
  • Group is preferable, and polyethylene glycol group and methyl polyethylene glycol group are more preferable.
  • R 201 in the general formula (I-II) may be either a hydrogen atom or a methyl group, but when R 202 is a hydrogen atom, it represents a methyl group.
  • R 202 in the general formula (I-II) is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group, and preferably having 1 to 20 carbon atoms substituted with a hydroxy group. Alkyl groups are particularly preferred.
  • Particularly preferred specific examples of the compound represented by the general formula (I) include, for example, methacrylic acid, (meth) acrylic acid-n-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 12 and R 13 of the general formula (II) include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). , An ethyl group, an n-propyl group and an isopropyl group are preferable, and an isopropyl group is more preferable.
  • dialkylaminoalkyl group having 3 to 9 carbon atoms in R 13 of the general formula (II) examples include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, A propylaminomethyl group, a dipropylaminoethyl group, a dipropylaminopropyl group, etc. are mentioned.
  • hydroxyalkyl group having 1 to 6 carbon atoms in R 13 of the general formula (II) those having a terminal portion substituted with a hydroxy group are preferred.
  • one in which one or two hydrogens are substituted with a hydroxy group is preferable, and one in which one hydrogen is substituted with a hydroxy group is more preferable.
  • those having 1 to 3 carbon atoms are preferred, and a straight chain is preferred.
  • a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group are preferable, and a hydroxyethyl group is more preferable.
  • R 11 in the general formula (II) is preferably a hydrogen atom.
  • R 12 in the general formula (II) is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 13 in the general formula (II) is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A hydrogen atom and an alkyl group having 1 to 3 carbon atoms are more preferable, and a hydrogen atom is particularly preferable.
  • the compound represented by the general formula (II) include compounds represented by the following general formula (II-I). (Wherein R 113 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, and R 11 and R 12 are the same as above).
  • Examples of the alkyl group having 1 to 6 carbon atoms and the hydroxyalkyl group having 1 to 6 carbon atoms in R 113 of the general formula (II-I) include the same as those in R 13 of the general formula (II), and are preferable. The same is true.
  • R 113 in formula (II-I) is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom.
  • More preferred specific examples of the compound represented by the general formula (II) include compounds represented by the following general formula (II-II). (Wherein R 212 and R 213 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 11 is the same as above).
  • Examples of the alkyl group having 1 to 3 carbon atoms in R 212 and R 213 in the general formula (II-II) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and an isopropyl group is preferable.
  • Particularly preferred specific examples of the compound represented by the general formula (II) include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide etc.
  • (Meth) acrylamide N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide (Meth) acrylamide is more preferable, and acrylamide is particularly preferable.
  • the compound represented by the general formula (II) may be commercially available or may be appropriately synthesized by a method known per se.
  • the combinations of the constituent components of the copolymer according to the present invention include combinations described in the following table, among which combinations 1 to 4 are preferable, combinations 1, 3 and 4 are more preferable, and combination 1 is particularly preferable. Furthermore, among the combinations 1, a combination comprising a monomer unit derived from acrylic acid and one monomer unit derived from the compound represented by the general formula (II) is preferable, and the monomer unit derived from acrylic acid and the general formula (I-II) The combination which consists of 1 type of monomer units derived from the compound shown by these is more preferable. More specifically, a combination comprising a monomer unit derived from acrylic acid and one kind of monomer unit derived from the compound listed as a particularly preferred specific example of the compound represented by formula (I) is preferable.
  • the content of polyacrylic acid in one or more polymers containing (A) polyacrylic acid is 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 75 to 100% by mass with respect to the total mass of (A). 100% by mass.
  • “100 mass%” here shows the case where the 1 or more types of polymer containing (A) polyacrylic acid is only (A1) polyacrylic acid.
  • One or more polymers including polyacrylic acid may be neutralized.
  • a polymer containing a monomer unit having a carboxy group as a constituent component among one or more polymers containing polyacrylic acid a part or all of the carboxy group in the polymer may be a salt.
  • a part or all of the carboxy group in the polymer may be a salt.
  • As one or more types of polymers containing polyacrylic acid those in which any one or more of the polymers are neutralized are preferable, and those in which at least polyacrylic acid is neutralized are more preferable. Preferably, all polymers are neutralized.
  • the one or more polymers containing polyacrylic acid are (A1) only polyacrylic acid, neutralized polyacrylic acid is preferred;
  • (A) one or more polymers containing polyacrylic acid are ( A2)
  • at least one polymer in the polymer group is neutralized, and at least polyacrylic acid is neutralized. More preferred are those obtained by neutralizing all polymers in the polymer group.
  • the neutralized polymer is preferably neutralized with an alkali metal such as sodium hydroxide, lithium hydroxide, or potassium hydroxide, and more preferably neutralized with sodium hydroxide.
  • the degree of neutralization at this time is usually 60 to 100%, preferably 70 to 100%, more preferably 70 to 90%.
  • One or more polymers containing polyacrylic acid may be cross-linked.
  • those in which any one or more of the polymers are cross-linked are preferable, and those in which at least polyacrylic acid is cross-linked are more preferable. More preferably, all polymers are crosslinked.
  • polymers containing polyacrylic acid are (A1) polyacrylic acid alone, crosslinked polyacrylic acid is preferred; (A) one or more polymers containing polyacrylic acid are (A2 )
  • a polymer group consisting of polyacrylic acid and one or more polymers other than polyacrylic acid it is preferable that at least one polymer in the polymer group is cross-linked, and at least polyacrylic acid is cross-linked Are more preferable, and those in which all the polymers in the polymer group are crosslinked are more preferable.
  • crosslinking agent used for crosslinking the polymer examples include a crosslinking agent selected from compounds described in the following general formulas [1] to [13] and a polymer described in the general formula [14] (hereinafter referred to as the present invention). May be abbreviated as a crosslinking agent). Further, the crosslinked polymer may be further neutralized.
  • the viscosity of the crosslinked polymer is usually 500 to 50,000 mPa ⁇ S, preferably 1,000 to 50,000 mPa ⁇ S when the rotational speed of the rotational viscometer is 12 rpm.
  • a rotational viscometer having an upper limit viscosity of 50,000 mPa ⁇ S at a rotational speed of 12 rpm was used.
  • the viscosity is a value obtained by dispersing (suspending) each polymer in water at a concentration of 1% by mass at 20 to 25 ° C. using a B-type rotational viscometer.
  • (A) As one or more types of polymers containing polyacrylic acid those in which at least one of the polymers is cross-linked by the cross-linking agent according to the present invention are preferred; More preferred are those crosslinked with the crosslinking agent according to the invention; more preferred are all the polymers crosslinked with the crosslinking agent according to the invention; and all the polymers are crosslinked with the crosslinking agent according to the invention and are neutralized. Particularly preferred are When (A) at least one polymer containing polyacrylic acid is only (A1) polyacrylic acid, polyacrylic acid crosslinked with the crosslinking agent according to the present invention is preferred; crosslinked with the crosslinking agent according to the present invention. And neutralized polyacrylic acid is more preferred.
  • At least one polymer containing polyacrylic acid is a polymer group comprising (A2) a polymer other than polyacrylic acid and at least one polyacrylic acid
  • at least one polymer in the polymer group is Those crosslinked by the crosslinking agent according to the present invention are preferred; at least polyacrylic acid is more preferably crosslinked by the crosslinking agent according to the present invention; all polymers in the polymer group are formed by the crosslinking agent according to the present invention. More preferred are those that have been cross-linked; more preferred are those in which all polymers in the group of polymers have been cross-linked and neutralized by the cross-linking agent according to the present invention.
  • the weight average molecular weight of each of the one or more polymers including polyacrylic acid is usually 1,000 to 10,000,000, preferably 10,000 to 5,000,000.
  • the polyacrylic acid alone in (A1) one or more polymers containing polyacrylic acid is preferably (A1-1) polyacrylic acid crosslinked with a crosslinking agent according to the present invention, (A1-2) Polyacrylic acid crosslinked and neutralized by the crosslinking agent according to the present invention is more preferred.
  • the polymer group consisting of polymers other than polyacrylic acid and one or more polyacrylic acids includes (A2-1) polyacrylic acid and one or more polymers.
  • (A2-3) Polymer group comprising polyacrylic acid and one or more copolymers And the copolymer is a copolymer containing a monomer unit derived from acrylic acid as a constituent component.
  • the copolymer is a copolymer containing a monomer unit derived from acrylic acid as a constituent, and at least in the polymer group
  • Particularly preferred are those comprising the copolymers according to the invention, with (A2-5) polyacrylic acid and the copolymers according to the invention being most preferred.
  • (A2-5) polyacrylic acid and the copolymer according to the present invention (A2-5-1) polyacrylic acid and the copolymer according to the present invention, and the polyacrylic acid and / or the copolymer according to the present invention are the present invention.
  • (A2-5-2) Polyacrylic acid and the copolymer according to the present invention are preferred, and at least polyacrylic acid is preferably crosslinked with the crosslinking agent according to the present invention.
  • polyacrylic acid and a copolymer according to the present invention wherein polyacrylic acid and the copolymer according to the present invention are more preferably cross-linked by a cross-linking agent according to the present invention;
  • Polyacrylic acid and the copolymer according to the present invention wherein the polyacrylic acid and the copolymer according to the present invention are bridged by the crosslinking agent according to the present invention.
  • the polyacrylic acid is at least neutralized with polyacrylic acid; (A2-5-5) cross-linked and neutralized with the cross-linking agent according to the present invention, and the cross-linking agent according to the present invention.
  • Particularly preferred are copolymers according to the invention which have been crosslinked and neutralized by
  • the one or more polymers containing polyacrylic acid are preferably the above (A1) and (A2-5), more preferably the above (A1-1) and (A2-5-1), and the above (A1 -1) and (A2-5-2) are more preferable, (A1-1) and (A2-5-3) are particularly preferable, and (A1-2) and (A2-5-5) are most preferable. .
  • Crosslinking agent according to the present invention (A) The crosslinking agent used for crosslinking one or more polymers containing polyacrylic acid is a compound selected from the compounds represented by the following general formulas [1] to [13] and the polymer represented by the following general formula [14]. Agents.
  • R 25 and R 26 each independently represent a hydrogen atom or a methyl group
  • R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1]
  • R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6
  • R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22).
  • R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms.
  • R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms, d represents an integer of 1 to 6, e represents an integer of 0 to 6, f and g Each independently represents an integer of 0 or 1.
  • R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group.
  • R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms.
  • ring Ar 1 represents a benzene ring or a naphthalene ring
  • R 49 represents an alkylene group having 1 to 6 carbon atoms
  • h represents an integer of 2 to 4
  • each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring, and R 50 represents an alkylene group having 1 to 6 carbon atoms.
  • Ar 4 represents a benzene ring or a naphthalene ring.
  • i represents an integer of 0 to 6.
  • R 51 represents an alkylene group having 1 to 6 carbon atoms.
  • R 52 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [12-1]
  • Group represented by (Wherein R 53 represents an alkyl group having 1 to 6 carbon atoms, R 54 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 5 represents a benzene ring or a naphthalene ring, j is Represents an integer of 0 to 4, or a group represented by the following general formula [12-2] (Wherein R 55 represents an alkylene group having 1 to 6 carbon atoms, and R 53 , R 54 , and rings Ar 5 and j are the same as above). ]
  • R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1] (Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5). ]
  • R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2] (Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3] (Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000. ]
  • a is preferably an integer of 1 to 3, and more preferably 1.
  • the compound represented by the general formula [1] include, for example, allyl acrylate (acrylic acid-2-propenyl), acrylic acid-3-butenyl, acrylic acid-4-pentenyl, acrylic acid-5-hexynyl, and acrylic acid. -6-heptenyl, -7-octenyl acrylate, and the like, and allyl acrylate is preferred.
  • the alkylene group having 1 to 20 carbon atoms in R 21 of the general formula [2] preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable.
  • methylene group ethylene group, methylmethylene group, trimethylene group, propylene group, dimethylmethylene group, ethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group Group, 2-ethyltrimethylene group, n-propylethylene group, isopropylethylene group, n-butylmethylene group, isobutylmethylene group, tert-butylmethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpenta Methylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 2-ethy
  • methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group are included.
  • a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are more preferable.
  • the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1] preferably has 1 to 3 carbon atoms, and more preferably has 2 to 3 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable.
  • a methylene group, an ethylene group, and a trimethylene group are preferable, an ethylene group and a trimethylene group are more preferable, and an ethylene group is particularly preferable.
  • an integer of 2 to 6 is preferable, and an integer of 4 to 6 is more preferable.
  • the b — (R 22 —O) — groups may be the same or different, and are preferably all the same.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 23 and R 24 of the general formula [2-2] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1].
  • the preferred ones are the same.
  • C in the general formula [2-2] is preferably an integer of 2 to 13, and more preferably an integer of 3 to 8.
  • the c — (R 23 —O) — groups may be the same or different, and are preferably all the same.
  • the compound represented by the general formula [2] include compounds represented by the following general formulas [2-01] to [2-14]. Among them, the general formulas [209] to [2-14] The compounds described in general formulas [2-11] and [2-12] are more preferable, and the compounds described in general formula [2-11] are particularly preferable. (Wherein b and c are the same as above, s represents an integer of 1 to 6, preferably an integer of 4 to 6, more preferably 6.)
  • Examples of the alkylene group having 1 to 3 carbon atoms in R 27 to R 33 in the general formula [3] include a methylene group, an ethylene group, and a trimethylene group.
  • a methylene group and an ethylene group are preferable, and a methylene group is more preferable.
  • the compound represented by the general formula [3] include, for example, compounds represented by the following formulas [3-01] to [3-03], and among them, a compound represented by the formula [3-01] is preferable.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 34 to R 37 of the general formula [4] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1], and are preferable. The same is true.
  • d in the general formula [4] an integer of 1 to 4 is preferable, and 1 or 2 is more preferable.
  • the d — (O—R 34 ) — groups may be the same or different, and are preferably the same.
  • an integer of 0 to 2 is preferable.
  • the e — (R 35 —O) — groups may be the same or different, and are preferably all the same.
  • — (R 35 —O) — represents a bond. That is, it represents that adjacent —O— and — (R 37 ) g — are directly bonded.
  • the bond means the same meaning.
  • f and g each independently represent an integer of 0 or 1, and it is preferable that f and g are the same.
  • f is 0, —R 36 — represents a bond
  • g is 0, —R 37 — represents a bond.
  • the compound represented by the general formula [4] include, for example, the compounds represented by the following general formula [4-1] or [4-2]. Among them, the compounds represented by the general formula [4-1] are exemplified. preferable.
  • R 64 and R 65 each independently represents a methylene group, an ethylene group or a trimethylene group, d ′ represents 1 or 2, and e ′ represents an integer of 0 to 2).
  • R 66 represents a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group or hexamethylene group, and d ′′ represents an integer of 1 to 4)
  • R 64 and R 65 in the general formula [4-1] are preferably ethylene groups.
  • d ′ and e ′ are preferably the same.
  • the d ′ — (O—R 64 ) — groups may be the same or different, and are preferably the same.
  • the e ′ — (R 65 —O) — groups may be the same or different, and are preferably the same.
  • e ′ is 0, — (R 65 —O) — represents a bond.
  • R 66 in the general formula [4-2] is preferably an ethylene group, a tetramethylene group, or a hexamethylene group.
  • d ′′ is preferably 1 or 2.
  • the d ′′ number of — (O—R 65 ) — groups may be the same or different, and are preferably all the same.
  • More preferred specific examples of the compound represented by the general formula [4] include, for example, compounds represented by the following formulas [4-01] to [4-10], among which the formulas [4-02] to [4-05] The compounds described above are preferred.
  • R 38 to R 45 in the general formula [5] at least two or more are vinyl groups or vinyl ketone groups, preferably 5 to 8 vinyl groups or vinyl ketone groups, and preferably 5 to 7 vinyl groups. Or what is a vinyl ketone group is more preferable.
  • Preferable specific examples of the compound represented by the general formula [5] include, for example, compounds represented by the following formulas [5-01] to [5-06].
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 46 to R 48 of the general formula [6] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1].
  • R 46 and R 48 in the general formula [6] are preferably a methylene group, an ethylene group, a trimethylene group, a propylmethylene group, a pentamethylene group and a hexamethylene group, and more preferably a methylene group, an ethylene group and a trimethylene group.
  • R 47 in the general formula [6] is preferably a cyclopentylene group or a cyclohexylene group, and more preferably a cyclohexylene group.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 49 of the general formula [7] include the same groups as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1].
  • An ethylene group is preferred, and a methylene group is more preferred.
  • the ring Ar 1 in the general formula [7] is preferably a benzene ring.
  • h in the general formula [7] an integer of 3 to 4 is preferable.
  • the h groups represented by the following formulas may be the same or different, and are preferably the same. (In the formula, R 49 is the same as above.)
  • Preferable specific examples of the compound represented by the general formula [7] include, for example, compounds represented by the following formulas [7-01] to [7-02].
  • a benzene ring is preferable.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 50 of the general formula [8] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1].
  • An ethylene group and a trimethylene group are preferable, and a trimethylene group is more preferable.
  • the compound represented by the general formula [8] include, for example, compounds represented by the following formulas [8-01] to [8-03], and among them, a compound represented by the formula [8-03] is preferable.
  • the ring Ar 4 in the general formula [9] is preferably a benzene ring.
  • the compound represented by the general formula [9] include, for example, compounds represented by the following formulas [9-01] and [9-02], and among them, a compound represented by the formula [9-01] is preferable.
  • I in the general formula [10] is preferably an integer of 0 to 3, more preferably 0.
  • the compound represented by the general formula [10] include, for example, divinylethylene glycol (1,5-hexadiene-3,4-diol), 1,6-heptadiene-3,5-diol, 1,7-octadiene. -3,6-diol, 1,8-nonadiene-3,7-diol and the like, and divinylethylene glycol is preferred.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 51 of the general formula [11] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1].
  • An ethylene group and a trimethylene group are preferable, and a methylene group is more preferable.
  • the compound represented by the general formula [11] include N, N′-methylenebisacrylamide, N, N′-ethylenebisacrylamide, N, N′-trimethylenebisacrylamide and the like. N'-methylenebisacrylamide is preferred.
  • the alkylene group having 1 to 6 carbon atoms of the “substituted or unsubstituted alkylene group having 1 to 6 carbon atoms” in R 52 of the general formula [12] is represented by R 22 in the general formula [2-1].
  • Examples thereof include the same alkylene groups having 1 to 6 carbon atoms, and among them, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable.
  • the above carbon number of 1 to 6 does not include the carbon number of the substituent.
  • the number of carbon atoms of a group having a substituent does not include the number of carbon atoms of the substituent.
  • arylene group having 6 to 10 carbon atoms of the “substituted or unsubstituted arylene group having 6 to 10 carbon atoms” in R 52 of the general formula [12] include, for example, a phenylene group and a naphthylene group. And a phenylene group is preferable.
  • alkylene group having 1 to 6 carbon atoms and the arylene group having 6 to 10 carbon atoms having a substituent in R 52 of the general formula [12] those having 1 or 2 substituents are preferable.
  • substituents include 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, and n-hexyl group.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, a propoxy group or a hexyloxy group
  • An alkoxy group having 6 to 10 carbon atoms such as a phenyl group; a hydroxyalkyl group having 1 to 6 carbon atoms such as a hydroxy
  • R 52 in the general formula [12] is preferably an unsubstituted alkylene group having 1 to 6 carbon atoms and an unsubstituted phenylene group having an alkyl group having 1 to 6 carbon atoms as a substituent.
  • An alkylene group having 1 to 6 carbon atoms is more preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 53 of the general formulas [12-1] and [12-2] include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). The preferred ones are the same.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 54 of the general formulas [12-1] and [12-2] and R 55 of the general formula [12-2] include R 22 of the general formula [2-1]. The same as the alkylene group having 1 to 6 carbon atoms in FIG.
  • the ring Ar 5 in the general formulas [12-1] and [12-2] is preferably a benzene ring.
  • J in general formulas [12-1] and [12-2] is preferably 0 or 1.
  • j is 0, it means that the benzene ring or naphthalene ring of the ring Ar 5 has no substituent.
  • the compound represented by the general formula [12] include compounds represented by the following general formulas [12-3] to [12-6], and among them, the compound represented by the general formula [12-6] is preferable. . (Wherein R 67 represents an unsubstituted alkylene group having 1 to 6 carbon atoms, and R 53 to R 55 and j are the same as described above.)
  • Examples of the unsubstituted alkylene group having 1 to 6 carbon atoms in R 67 of the general formula [12-6] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. Of these, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable.
  • Preferred examples of the compound represented by the general formula [12-6] include 1,2: 4,5-diepoxypentane, 1,2: 5,6-diepoxyhexane, 1,2: 6,7-di- Examples thereof include epoxy heptane, 1,2: 7,8-diepoxyoctane, 1,2: 8,9-diepoxynonane, 1,2: 9,10-diepoxydecane, and the like.
  • Examples of the alkyl group having 1 to 6 carbon atoms of the “substituted or unsubstituted alkyl group having 1 to 6 carbon atoms” in R 56 and R 57 of the general formula [13] include R 4 of the general formula (IV). The same as the alkyl group having 1 to 6 carbon atoms in FIG.
  • aryl group having 6 to 10 carbon atoms of the “substituted or unsubstituted aryl group having 6 to 10 carbon atoms” in R 56 and R 57 of the general formula [13] include a phenyl group, A naphthyl group etc. are mentioned, A phenyl group is preferable.
  • the alkyl group having 1 to 6 carbon atoms having a substituent and the aryl group having 6 to 10 carbon atoms having a substituent in R 56 and R 57 in the general formula [13] have 1 to 3 substituents Are preferred, and those having two substituents are more preferred. Examples of the substituent are the same as the specific examples of the substituent of R 52 in the general formula [12] “the alkylene group having 1 to 6 carbon atoms having a substituent and the arylene group having 6 to 10 carbon atoms having a substituent”. Things.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 58 of the general formula [13-1] include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). It is.
  • Examples of the alkylene group having 1 to 6 carbon atoms in R 59 of the general formula [13-1] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. Is the same.
  • the ring Ar 6 in the general formula [13-1] is preferably a benzene ring.
  • k is preferably an integer of 1 to 3, and more preferably 2. When k is 0, it means that the benzene ring or naphthalene ring of the ring Ar 6 has no substituent.
  • R 56 and R 57 in the general formula [13] it is preferable that R 56 and R 57 are the same, a phenyl group having an alkyl group having 1 to 6 carbon atoms as a substituent, or a general formula The group represented by [13-1] is preferred.
  • the compound represented by the general formula [13] include the compounds represented by the following general formulas [13-2] and [13-3], and among them, the compounds represented by the general formula [13-2] are preferable. .
  • R 58 , R 59 and k are the same as above, and two R 58 and R 59 may be the same or different.
  • Preferable specific examples of the compound represented by the general formula [13-2] include compounds represented by the following formulas [13-01] to [13-12].
  • Examples of the substituted or unsubstituted alkylene group having 1 to 6 carbon atoms and the substituted or unsubstituted arylene group having 6 to 10 carbon atoms in R 60 of the general formula [14] include those represented by the general formula [12 the same thing can be mentioned as those in R 52 in.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 61 of the general formulas [14-1] to [14-3] include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). It is done.
  • R 62 of the general formulas [14-1] to [14-3] and R 63 of the general formula [14-3] is represented by R 22 in the general formula [2-1]. Examples thereof are the same as the alkylene group having 1 to 6 carbon atoms.
  • the ring Ar 7 in the general formulas [14-1] to [14-3] is preferably a benzene ring.
  • p is preferably 0 or 1.
  • p is 0, it means that the benzene ring or naphthalene ring of the ring Ar 7 has no substituent.
  • R 60 in the general formula [14] is preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenylene group, and unsubstituted 1 to 6 carbon atoms.
  • An alkylene group and a phenylene group having a substituent are more preferable, and a phenylene group having an alkyl group having 1 to 6 carbon atoms as a substituent is particularly preferable.
  • M in the general formula [14] is preferably an integer of 10 to 1,000, and more preferably an integer of 10 to 100.
  • polymers represented by the general formula [14] include polymers represented by the following general formulas [14-4] to [14-8], and among them, the polymer represented by the general formula [14-5] is preferable. .
  • R 61 to R 63 , p and m are the same as above, and R 68 represents an unsubstituted alkylene group having 1 to 6 carbon atoms.
  • the unsubstituted alkylene group having 1 to 6 carbon atoms in R 61 of the general formula [14-2] is the same as the unsubstituted alkylene group having 1 to 6 carbon atoms in R 67 of the general formula [12-6]. And preferred examples are also the same.
  • Preferred specific examples of the polymer represented by the general formula [14-5] include polymers represented by the following general formulas [14-01] to [14-04], and the polymers represented by the general formula [14-01] preferable. (Wherein m is the same as above)
  • crosslinking agent compounds represented by the general formulas [2], [3], [4], [9], [10] and [11] and a polymer represented by the general formula [14] are preferable.
  • the compounds described in the formulas [2], [3], [4] and [10] are more preferable, the compounds described in the general formulas [2] and [4] are more preferable, and the compounds described in the general formula [2] are particularly preferable.
  • the cross-linking agent may be a commercially available one, or one appropriately synthesized by a method known per se.
  • polymers containing polyacrylic acid may be produced by performing a polymerization reaction according to a method known per se.
  • polyacrylic acid can be produced by polymerizing acrylic acid, if necessary, in the presence of a polymerization initiator.
  • the polymerization reaction may be carried out according to a method known per se. Specifically, it is usually 30 to 200 ° C., preferably 70 to 180 ° C., more preferably 80 to 150 ° C. in a suitable solvent, usually 0
  • the reaction may be performed for 1 to 24 hours, preferably 1 to 10 hours.
  • the polymerization initiator is not particularly limited as long as it is usually used in this field.
  • 2,2′-azobis isobutyronitrile
  • 2,2′-azobis (2,4-dimethylvalero) Nitrile 2,2'-azobis (2-methylpropionate)
  • 2,2'-azobis (2-methylbutyronitrile) benzoyl peroxide, lauroyl peroxide, etc.
  • -Azobis isobutyronitrile
  • the amount of the polymerization initiator used is usually 0.01 to 30% by mass with respect to the total amount of the reaction product.
  • the solvent is not particularly limited as long as it is usually used in this field, and examples thereof include toluene, 1,4-dioxane, tetrahydrofuran, isopropanol, methyl ethyl ketone, propylene glycol monomethyl ether acetate and the like, among which propylene glycol monomethyl Ether acetate is preferred. These may be used alone or in combination of two or more.
  • the amount of the solvent used is 1 to 10 times the volume of the total volume of the reaction product.
  • the product obtained after the above polymerization reaction may be subjected to general post-treatment operations and purification operations usually performed in this field, if necessary. Specifically, for example, filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, column chromatography and the like may be performed.
  • the polymer other than polyacrylic acid in (A2) may be produced by appropriately setting a monomer in accordance with a desired polymer and performing a reaction in the same manner as the polyacrylic acid polymerization reaction described above.
  • the copolymer according to the present invention can be produced by adding one or two compounds represented by the general formula (I) or the general formula (II) in addition to acrylic acid in the polymerization reaction described above.
  • the reaction conditions type and amount of polymerization initiator, type and amount of solvent, reaction temperature, reaction time, etc.
  • the amount of the compound represented by the general formula (I) or the general formula (II) used in the polymerization reaction of the copolymer according to the present invention is such that the monomer unit derived from acrylic acid in the copolymer according to the present invention and the general formula (I) Or what is necessary is just to set suitably so that it may become a mass ratio of the monomer unit derived from the compound shown by general formula (II).
  • the polymer to be neutralized may be crosslinked or may be crosslinked after neutralization.
  • Examples of the solvent used for neutralization include the same solvents as those used in the polymerization reaction described above.
  • the cross-linking agent according to the present invention may be used according to a method known per se.
  • the polymerization reaction and the crosslinking reaction may be performed simultaneously by adding a crosslinking agent selected from the compounds described in the general formulas [1] to [11] in the polymerization reaction described above.
  • the obtained polymer and the compound represented by the general formula [12] or [13] or the polymer represented by the general formula [14] are reacted under the same reaction conditions (solvents) as the polymerization reaction described above. And the amount used, reaction temperature, reaction time, etc.).
  • the amount of the compounds represented by the general formulas [1] to [11] is usually 0.001 to 10 mol%, preferably 0.005 to 1 mol%, more preferably 0.01 to 0, based on 1 mol of the monomer used. .5 mol%.
  • the amount of the compound represented by the general formula [12] or [13] or the polymer represented by the general formula [14] is usually 0.01 to 40% by mass, preferably 0.8%, based on the mass of the polymer to be crosslinked. 05 to 20% by mass, more preferably 0.1 to 10% by mass.
  • the cross-linked polyacrylic acid is prepared as follows. That is, 2,2′-azobis (isobutyric acid) and acrylic acid and 0.01 to 0.5 mol% of a crosslinking agent selected from the compounds represented by the general formulas [1] to [11] with respect to 1 mol of acrylic acid.
  • a polymerization initiator such as (ronitrile)
  • it is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume.
  • a polymerization reaction and a crosslinking reaction are carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked polyacrylic acid.
  • 0.5-1 mol of an alkali metal such as sodium hydroxide may be added to 1 mol of the carboxy group of the obtained crosslinked polyacrylic acid to form a crosslinked polyacrylate.
  • a polyacrylic acid having a weight average molecular weight of 10,000 to 5,000,000 and a compound represented by the general formula [12] or [13] or 0.1 to 10% by mass relative to the mass of the polyacrylic acid or the general formula [14] The polymer is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a crosslinking reaction is carried out at 80 to 150 ° C.
  • a crosslinked polyacrylic acid for 0.1 to 10 hours to prepare a crosslinked polyacrylic acid. Further, if necessary, 0.5-1 mol of an alkali metal such as sodium hydroxide may be added to 1 mol of the carboxy group of the obtained crosslinked polyacrylic acid to form a crosslinked polyacrylate.
  • an alkali metal such as sodium hydroxide
  • the crosslinked copolymer according to the present invention is specifically prepared as follows. That is, with respect to acrylic acid, 70 to 30 parts by mass of the compound represented by the general formula (I) or general formula (II) with respect to 30 to 70 parts by mass of acrylic acid, and 1 mol of the monomer used. 0.01 to 0.5 mol% of a crosslinking agent selected from the compounds represented by the general formulas [1] to [11] in the presence of a polymerization initiator such as 2,2′-azobis (isobutyronitrile), It is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume.
  • a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume.
  • a polymerization reaction and a crosslinking reaction are carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked copolymer according to the present invention.
  • an alkali metal such as sodium hydroxide is added to 1 mol of the carboxy group of the obtained cross-linked copolymer according to the present invention to cross-link the copolymer salt according to the present invention. It is good.
  • acrylic acid and 70 to 30 parts by mass of the compound represented by the general formula (I) or the general formula (II) with respect to 30 to 70 parts by mass of acrylic acid are combined with 2,2′-azobis.
  • a polymerization initiator such as (isobutyronitrile)
  • a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume.
  • a polymerization reaction is carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a copolymer according to the present invention.
  • the obtained copolymer according to the present invention and 0.1 to 10% by mass of the compound of the general formula [12] or [13] or the polymer of the general formula [14] with respect to the mass of the copolymer It is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a crosslinking reaction is carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked copolymer according to the present invention.
  • a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume.
  • the (B) divalent to 10-valent alcohol (hereinafter sometimes abbreviated as the alcohol according to the present invention) is a conventionally known alcohol that is usually used in this field.
  • the divalent to hexavalent ones are preferable, and the divalent to tetravalent ones are more preferable.
  • R 71 represents an alkylene group having 1 to 6 carbon atoms
  • R 72 represents a hydroxy group or a hydroxyalkyl group having 1 to 6 carbon atoms
  • R 73 represents a hydrogen atom, 1 to 6 carbon atoms Or an alkyl group having 1 to 6 carbon atoms
  • R 74 represents an alkylene group having 1 to 6 carbon atoms which may have —O— in the chain
  • r represents 0 to 4 carbon atoms.
  • the alkylene group having 1 to 6 carbon atoms in R 71 of the general formula (B1) is preferably one having 3 to 6 carbon atoms when r is 0, and one having 1 to 6 carbon atoms when r is an integer of 1 to 4. 4 is preferred. Moreover, it may be any of linear, branched and cyclic, preferably linear and branched, and more preferably linear.
  • methylene group ethylene group, methylmethylene group, trimethylene group, propylene group, dimethylmethylene group, ethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, hexamethylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, etc.
  • a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable.
  • a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are more preferable, and when r is an integer of 1 to 4, a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are more preferable.
  • Examples of the hydroxyalkyl group having 1 to 6 carbon atoms in R 72 and R 73 of the general formula (B1) include the same as the hydroxyalkyl group having 1 to 6 carbon atoms in R 13 of the general formula (II).
  • a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, and a hydroxymethyl group and a hydroxyethyl group are more preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 73 of the general formula (B1) include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV).
  • N-propyl group and n-butyl group are preferable, and methyl group and ethyl group are more preferable.
  • the alkylene group having 1 to 6 carbon atoms which does not have —O— in the chain in R 74 of the general formula (B1) is the same as the alkylene group having 1 to 6 carbon atoms in R 71 of the general formula (B1).
  • a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable
  • a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are more preferable
  • a methylene group and an ethylene group are preferable. Particularly preferred.
  • Examples of the alkylene group having 1 to 6 carbon atoms and having —O— in the chain of R 74 in the general formula (B1) include groups represented by the following general formula (B1-1).
  • R 75 and R 76 each independently represents a linear or branched alkylene group having 1 to 5 carbon atoms, and t represents an integer of 1 to 5, provided that The total number of carbon atoms is 2 to 6, and t R75s may be the same or different.
  • alkylene group having 1 to 5 carbon atoms in R 75 and R 76 in the general formula (B1-1) those having 1 to 3 carbon atoms are preferable.
  • either linear or branched may be sufficient and a linear thing is more preferable.
  • Preferred specific examples of the group represented by the general formula (B1-1) include a group represented by the following general formula (B1-2).
  • R 75 ′ and R 76 ′ each independently represents a linear alkylene group having 1 to 5 carbon atoms, provided that the total number of carbon atoms in the formula is 2 to 6).
  • linear alkylene group having 1 to 5 carbon atoms in R 75 ′ and R 76 ′ of the general formula (B1-2) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
  • a methylene group and an ethylene group are preferable.
  • Specific examples of the group represented by the general formula (B1-2) include -CH 2 -O-CH 2- , -CH 2 -O-CH 2 CH 2- , -CH 2 -O-CH 2 CH 2 CH 2- , -CH 2 -O-CH 2 CH 2 CH 2 CH 2- , -CH 2 -O-CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 -O-CH 2 CH 2 CH 2- , -CH 2 CH 2 -O-CH 2 CH 2 CH 2- , -CH 2 CH 2 -O-CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 CH
  • R 72 in the general formula (B1) a hydroxy group and a linear hydroxyalkyl group having 1 to 6 carbon atoms are preferable, and a linear group in which a hydroxy group and one hydrogen at a terminal portion are substituted with a hydroxy group are used. And a straight-chain hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen atom in the terminal portion is substituted with a hydroxy group is particularly preferable.
  • a hydroxy group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, a hydroxy group, a hydroxymethyl group, and a hydroxyethyl group are more preferable, and a hydroxymethyl group and a hydroxyethyl group are particularly preferable.
  • R 73 in formula (B1) is preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a linear hydroxyalkyl group having 1 to 6 carbon atoms.
  • a linear alkylalkyl group having 1 to 6 carbon atoms in which an alkyl group having 1 to 6 carbon atoms and one hydrogen at a terminal portion are substituted with a hydroxy group is more preferable, and one hydrogen at a terminal portion is a hydroxy group.
  • a straight-chain C1-C6 hydroxyalkyl group substituted with is particularly preferred.
  • a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, and a hydrogen atom, a methyl group, an ethyl group, A hydroxymethyl group and a hydroxyethyl group are more preferable, and a hydroxymethyl group and a hydroxyethyl group are particularly preferable.
  • R 74 in the general formula (B1) is preferably a linear or branched alkylene group having 1 to 6 carbon atoms and a group represented by the general formula (B1-1).
  • the alkylene group of 6 and the group represented by the general formula (B1-2) are more preferable, and a linear alkylene group having 1 to 6 carbon atoms is particularly preferable.
  • methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, -CH 2 -O-CH 2- , -CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2- are preferred, methylene group, ethylene group, trimethylene group, tetramethylene group, -CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2- Is more preferable, methylene group, ethylene group, -CH 2 -O-CH 2 -is more preferable, A methylene group and an ethylene group are particularly preferable.
  • R in the general formula (B1) is preferably an integer of 0 to 2, more preferably 0 or 1.
  • the compound represented by the general formula (B1) include a compound represented by the following general formula (B2).
  • R 71 ⁇ R 73, R 75, R 76 and t are as defined above, R 77 represents a linear or branched alkylene group having 1 to 6 carbon atoms, r 2 represents 0 or 1, represents r 1 is 0 when r 2 is 0, r 1 when r 2 is 1 represents an integer of 0-3.
  • a plurality of R 72, R 73, R 75 , R 76 and t may be the same or different.
  • Examples of the linear or branched alkylene group having 1 to 6 carbon atoms in R 77 of the general formula (B2) include specific examples of the alkylene group having 1 to 6 carbon atoms in R 71 of the general formula (B1). Examples include straight-chain or branched ones. Among them, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable, and a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are preferable. More preferred are a methylene group and an ethylene group.
  • R 75 ′ and R 76 ′ are the same as above, R 71 ′ and R 77 ′ represent a linear alkylene group having 1 to 6 carbon atoms, and R 72 ′ represents a hydroxy group Or a linear hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen atom in the terminal portion is substituted with a hydroxy group, and R 73 ′ represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms Represents a straight-chain hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen in a group or a terminal portion is substituted with a hydroxy group, and r 3 represents an integer of 1 to 3, provided that R 75 ′ and The total number of carbon atoms of R 76 ′ is 2 to 6, and a plurality of R 72 ′, R 73 ′, R
  • linear alkylene group having 1 to 6 carbon atoms in R 71 ′ of the general formulas (B3) to (B5) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, A hexamethylene group is mentioned.
  • trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group are preferable.
  • general formula (B4) methylene group, ethylene group, trimethylene group and tetramethylene group are preferable.
  • (B5) a methylene group and an ethylene group are preferable.
  • linear alkylene group having 1 to 6 carbon atoms in R 77 ′ of the general formulas (B4) and (B5) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, A hexamethylene group can be mentioned, among which a methylene group, an ethylene group, a trimethylene group and a tetramethylene group are preferable, and a methylene group and an ethylene group are more preferable.
  • Examples of the linear hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen at a terminal portion in R 72 ′ and R 73 ′ in the general formulas (B4) and (B5) is substituted with a hydroxy group include Include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, and hydroxyhexyl group. Among them, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, and hydroxybutyl group are preferable. And a hydroxyethyl group is more preferable.
  • linear alkyl group having 1 to 6 carbon atoms in R 73 ′ of the general formulas (B4) and (B5) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n -Pentyl group and n-hexyl group can be mentioned, among which methyl group, ethyl group, n-propyl group and n-butyl group are preferable, and methyl group and ethyl group are more preferable.
  • R 72 ′ in formula (B4) is preferably a hydroxy group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group, more preferably a hydroxy group, a hydroxymethyl group or a hydroxyethyl group, and a hydroxymethyl group A hydroxyethyl group is particularly preferred.
  • R 73 ′ in the general formula (B4) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, or a hydroxybutyl group.
  • An atom, a methyl group, an ethyl group, a hydroxymethyl group, and a hydroxyethyl group are more preferable, and a hydroxymethyl group and a hydroxyethyl group are particularly preferable.
  • R 72 ′ and R 73 ′ in the general formula (B5) a linear hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen at a terminal portion is substituted with a hydroxy group is preferable.
  • a hydroxymethyl group and a hydroxyethyl group are preferred.
  • Preferred specific examples of the compound represented by the general formula (B3) include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
  • 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, and pentaerythritol are preferable.
  • 6-hexanetriol, trimethylolpropane, and pentaerythritol are more preferable, and pentaerythritol is particularly preferable.
  • Specific examples of the compound represented by the general formula (B5) include dipentaerythritol, tripentaerythritol, and tetrapentaerythritol, and dipentaerythritol is preferable.
  • the alcohol according to the present invention includes 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol, dipentaerythritol are preferred, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1 2,6-hexanetriol and pentaerythritol are more preferred, and pentaerythritol is particularly preferred.
  • the alcohol according to the present invention may be a commercially available one, or one appropriately synthesized by a method known per se.
  • the binder composition of the present invention comprises (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water. Note that (B) divalent to 10-valent alcohols may be used alone or in combination of two or more, and preferably only one is used.
  • the content of one or more polymers including (A) polyacrylic acid in the binder composition of the present invention is based on the total mass of (A) and (B) in the binder composition of the present invention. It is 70 to 99% by mass, preferably 75 to 99% by mass, and more preferably 80 to 99% by mass. In addition, when (A) is 2 or more types of polymers, those total mass should just become said content.
  • the content of the (B) divalent to 10-valent alcohol in the binder composition of the present invention is 1 to 30 relative to the total mass of (A) and (B) in the binder composition of the present invention. % By mass, preferably 1 to 25% by mass, more preferably 1 to 20% by mass. In addition, when using (B) combining 2 or more types, those total mass should just become said content.
  • the content of (C) water in the binder composition of the present invention is such that the total mass of (A) and (B) in the binder composition of the present invention is 1 to 50% by mass, preferably 1 It is an amount that becomes ⁇ 20 mass%.
  • the concentration of the one or more polymers containing (A) polyacrylic acid in the binder composition of the present invention may be appropriately set according to the concentration used for electrode preparation. 30%, preferably 1 to 20%.
  • the binder composition of the present invention is such that (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water have the above contents. It can be produced by mixing. At this time, (A) the polymerization reaction, neutralization treatment and crosslinking reaction in the method for producing one or more polymers containing polyacrylic acid need to be carried out in advance before producing the binder composition of the present invention.
  • the polymer (B) After carrying out the above-described polymerization reaction and, if necessary, neutralization treatment and / or cross-linking reaction to produce one or more kinds of polymers containing the desired (A) polyacrylic acid, the polymer (B) It is necessary to produce the binder composition of the present invention by mixing with divalent to 10-valent alcohol and (C) water. This is because, for example, in the above-described method (A) for producing one or more polymers containing polyacrylic acid, when (B) a divalent to 10-valent alcohol is added and a polymerization reaction is performed, the resulting polymer contains water. This is because there is a problem that it does not dissolve in various solvents such as the beginning, and the polymer cannot be used for electrode preparation.
  • the binder composition of the present invention is produced by bonding (A) one or more polymers containing polyacrylic acid via (B) a divalent to 10-valent alcohol at the time of electrode preparation (the alcohol is a linking agent). It is believed that the polymer is evenly disposed on the electrode and envelops the active material surface.
  • (A) one or more polymers containing polyacrylic acid is a polymer group comprising (A2) polyacrylic acid and one or more polymers other than polyacrylic acid. It is considered that it is possible to prevent phase separation during electrode preparation by bonding between polymers having different alcohols (for example, polyacrylic acid and the copolymer according to the present invention). Therefore, if an electrode is produced using the binder composition of the present invention, an electrode having excellent cycle characteristics that can utilize most of the active material surface for charge and discharge can be obtained.
  • the active material containing silicon in the slurry composition of the present invention is not limited as long as it contains at least silicon. Even if it is made of only silicon, it is made of active material other than silicon and silicon. Also good.
  • silicon in addition to silicon, SiO, silicon oxides such as SiO 2, silicon bonded to a metal (SiM: M is magnesium, iron, calcium, cobalt, nickel, boron, copper, manganese, silver, vanadium, Metal such as cerium and zinc), and silicon and silicon oxide are preferable, and silicon is more preferable.
  • the silicon may be one in which part or all of the surface is coated with carbon.
  • silicon whose surface is coated with carbon silicon oxide whose surface is coated with carbon, silicon bonded with a metal whose surface is coated with carbon, and the like can be given.
  • Examples of the active material other than silicon include carbon, germanium, tin, lead, zinc, aluminum, indium, antimony, bismuth, and the like. Among these, carbon is preferable.
  • Examples of the carbon include graphite-based carbon materials (graphite) such as natural graphite, artificial graphite, and expanded graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, and hard carbon. Of these, graphite such as natural graphite, artificial graphite, and expanded graphite is preferable.
  • Examples of the natural graphite include flaky graphite and massive graphite.
  • Examples of the artificial graphite include massive graphite, vapor-grown graphite, flaky graphite, and fibrous graphite.
  • Examples of the active material containing silicon in the slurry composition of the present invention include silicon, silicon oxide, silicon bonded to a metal, a mixture of two or more selected from these, or at least one of these and carbon. , An active material containing a mixture of at least one selected from germanium, tin, lead, zinc, aluminum, indium, antimony, and bismuth.
  • an active material containing silicon; silicon oxide; silicon bonded to metal; a mixture of two or more selected from these; or a mixture of at least one of these and carbon and / or tin Preferably, silicon; silicon oxide; silicon bonded to metal; or an active material containing a mixture of carbon, silicon, silicon oxide or silicon bonded to metal is more preferable, and silicon; An active material containing silicon oxide; or a mixture of at least two of carbon, silicon, or silicon oxide is more preferred, and an active material containing silicon and / or silicon oxide is particularly preferred.
  • the average particle size of the active material containing silicon in the slurry composition of the present invention varies depending on the type of active material, but is usually 1 nm to 100 ⁇ m, preferably 1 nm to 50 ⁇ m, more preferably 1 nm to 20 ⁇ m. .
  • the silicon content in the active material containing silicon in the slurry composition of the present invention is usually 10 to 100% by mass, preferably 40 to 100% by mass, and more preferably 50 to 100% by mass.
  • Examples of the conductive auxiliary in the slurry composition of the present invention include carbon blacks such as acetylene black, ketjen black, furnace black, and thermal black. Among them, acetylene black and ketjen black are preferable, and acetylene black is more preferable.
  • the slurry composition of the present invention is a composition for producing an electrode comprising 1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a binder composition of the present invention.
  • the slurry composition of the present invention may be used for preparing an anode or a negative electrode, but is preferably used for preparing a negative electrode.
  • the content of the active material containing silicon in the slurry composition of the present invention is 1 to 98% by mass, preferably 10 to 98% by mass, based on the mass of the slurry composition not containing the solvent.
  • the content of the conductive assistant in the slurry composition of the present invention is 1 to 40% by mass, preferably 1 to 30% by mass, more preferably 1 to 20% by mass with respect to the mass of the slurry composition not containing the solvent. is there.
  • the content of the binder composition of the present invention in the slurry composition of the present invention is 1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably based on the mass of the slurry composition not containing a solvent. 1 to 20% by mass.
  • the slurry composition of the present invention includes 1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a binder composition of the present invention, for example, a supporting salt, an ion conductive polymer, a binder polymer, and the like.
  • a supporting salt for example, Li (C 2 F 5 SO 2 ) 2 N (LiBETI), LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
  • Examples of the ion conductive polymer include polyethylene oxide (PEO) -based polymers and polypropylene oxide (PPO) -based polymers.
  • Examples of the binder polymer include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), styrene butadiene copolymer (SBR), acrylonitrile butadiene copolymer (NBR), and polyacrylonitrile (PAN). ), Ethylene vinyl alcohol copolymer (EVOH), polyurethane, polyacrylate, polyvinyl ether, polyimide and the like.
  • the contents of the supporting salt, the ion conductive polymer and the binder polymer may be set according to the amounts usually used in this field.
  • slurry composition of the present invention 1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a binder composition of the present invention are mixed in an appropriate solvent so as to be within the above-mentioned concentration range.
  • the solvent include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, ⁇ -butyrolactone, toluene, methyl ethyl ketone, ethyl acetate, dioxane and the like.
  • NMP N-methyl-2-pyrrolidone
  • dimethylformamide dimethylacetamide
  • methylformamide dimethylsulfoxide
  • acetonitrile acetonitrile
  • tetrahydrofuran ⁇ -butyrolactone
  • toluene methyl ethyl ketone
  • the current collector according to the present invention includes a foil, a mesh, an expanded grid (expanded metal), a punched metal, and the like using a conductive material such as nickel, copper, and stainless steel (SUS).
  • the mesh opening, wire diameter, number of meshes and the like are not particularly limited, and conventionally known ones can be used.
  • the preferred thickness of the current collector is 5 to 30 ⁇ m. However, a current collector having a thickness outside this range may be used.
  • the size of the current collector is determined according to the intended use of the battery. If a large electrode used for a large battery is manufactured, a current collector having a large area is used. If a small electrode is produced, a current collector with a small area is used.
  • the electrode of the present invention has 1) an active material containing silicon, 2) a conductive additive, 3) a binder derived from the binder composition of the present invention, and 4) a current collector. Specifically, it has a current collector and an active material layer formed on the surface thereof, including an active material containing silicon, a conductive additive, and a binder derived from the binder composition of the present invention. It is.
  • the electrode of the present invention can be used as a negative electrode or an anode, but is preferably used as a negative electrode.
  • the binder derived from the binder composition of the present invention uniformly disperses the active material containing silicon and the conductive additive on the current collector, and has good coverage. Therefore, the electrode of the present invention is excellent in reversibility.
  • the thickness of the active material layer (the thickness of the coating layer) is usually 1 to 500 ⁇ m, preferably 1 to 300 ⁇ m, more preferably 1 to 150 ⁇ m.
  • a method for producing an electrode of the present invention comprises a slurry composition [1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a composition containing the binder composition of the present invention] as a current collector. It is characterized by being coated on top and dried.
  • the slurry composition of the present invention is dried, so that (A) one or more kinds of polymers including polyacrylic acid in the binder composition of the present invention are converted into (B) a divalent to 10-valent alcohol.
  • the amount of the slurry composition of the present invention used may be appropriately set so that the thickness of the active material layer is within the above range after drying.
  • a self-propelled coater for example, an ink jet method, a doctor blade method, a spray method, or a combination thereof may be used. It can. Among these, a doctor blade method and an ink jet method capable of forming a thin layer are preferable, and a doctor blade method is more preferable.
  • the drying method in the method for producing an electrode of the present invention may be performed according to a method known per se, and is usually performed by heat treatment.
  • the drying conditions during heating may be appropriately set according to the coating amount and volatilization rate of the slurry composition of the present invention. Specifically, for example, it may be dried at 80 to 150 ° C., preferably 120 to 150 ° C. in a vacuum, usually for 5 to 20 hours, preferably 6 to 12 hours.
  • press treatment may be performed after drying.
  • the pressing method may be performed according to a method known per se, and examples thereof include a calender roll method and a flat plate press, and the calender roll method is preferable.
  • the electrode of the present invention can be used for a lithium battery, and can be used for any ordinary battery including a positive electrode, an electrolyte, and a negative electrode.
  • Examples of the electrolyte include vinylene carbonate, fluorovinylene carbonate, methyl vinylene carbonate, fluoromethyl vinylene carbonate, ethyl vinylene carbonate, propyl vinylene carbonate, butyl vinylene carbonate, dipropyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5 -Those having additives such as diethyl vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, phenyl ethylene carbonate, diallyl carbonate, fluoroethylene carbonate (FEC), catechol carbonate, 1,3-propane sultone and butane sultone are preferred. Those having ethylene carbonate (FEC) are more preferred.
  • the content of the additive in the electrolyte is usually 0.5% to 15%, preferably 0.5 to 5%.
  • Synthesis Example 1 Synthesis of crosslinked copolymer C-1 In a 200 mL round bottom flask equipped with a stirring device, a cooling tube, a thermometer, a nitrogen introduction tube and a dropping device, 70 g of propylene glycol monomethyl ether acetate (530 mmol, Wako Pure Chemical Industries, Ltd. )) And heated under a nitrogen stream until the internal temperature reached 90 ° C.
  • Synthesis Example 2 Synthesis of Non-Crosslinked Copolymer C-2 A non-crosslinked copolymer C-2 was obtained by subjecting it to a polymerization reaction in the same manner as in Synthesis Example 1 except that polyethylene glycol diacrylate was not added.
  • Synthesis Example 3 Synthesis of crosslinked homopolymer A-1 The same as Synthesis Example 1 except that 18.4 g (255 mmol) of acrylic acid was used instead of 9.2 g (128 mmol) without adding 2-hydroxyethyl acrylate. The polymer was subjected to a polymerization reaction to obtain a crosslinked homopolymer A-1.
  • Synthesis Example 4 Synthesis of Crosslinked Homopolymer A-2 Acrylic acid instead of 9.2 g (128 mmol) was added with 18.4 g (255 mmol) of 2,2′-azobis (isobutylnitrile) without adding 2-hydroxyethyl acrylate was subjected to a polymerization reaction in the same manner as in Synthesis Example 1 except that 0.2 g (1 mmol) was used instead of 0.04 g (0.2 mmol) to obtain a crosslinked homopolymer A-2.
  • Synthesis Example 6 Preparation of Non-crosslinked Copolymer Solution H-6 Neutralized non-crosslinked by the same method as Synthesis Example 5 except that 4.6 g of non-crosslinked copolymer C-2 was used instead of 4.6 g of crosslinked copolymer C-1 A solution of copolymer was obtained (degree of neutralization 80%). This was designated as non-crosslinked copolymer solution H-6.
  • Synthesis Example 8 Preparation of Cross-linked Homopolymer Solution H-1 Neutralized cross-linking by the same method as in Synthetic Example 7 except that 3.8 g of cross-linked homopolymer A-2 was used instead of 3.8 g of cross-linked homopolymer A-1. A homopolymer solution was obtained (degree of neutralization 80%). This was designated as a crosslinked homopolymer solution H-1.
  • Mw weight average molecular weight
  • Synthesis Example 10 Preparation of non-crosslinked homopolymer solution H-4 Except for using 3.8 g of polyacrylic acid having a weight average molecular weight of 1,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.) instead of 3.8 g of polyacrylic acid having a weight average molecular weight of 250,000 Obtained a neutralized non-crosslinked homopolymer solution by the same method as in Synthesis Example 9 (degree of neutralization 80%). This was designated as non-crosslinked homopolymer solution H-4.
  • Synthesis Example 11 Preparation of binder solution K-1 In a 10 mL beaker made of Teflon (registered trademark), 8.9 g of a crosslinked homopolymer solution H-2 (0.89 g as a solid content) and 1 g of a crosslinked copolymer solution H-5 (0.1 g as a solid content) ), 0.01 g of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) and 90 ⁇ L of ion-exchanged water were added and stirred until a transparent solution was obtained to obtain a binder solution K-1 having a solid content of 10 wt%.
  • Teflon registered trademark
  • pentaerythritol manufactured by Wako Pure Chemical Industries, Ltd.
  • Binder Solution K-2 Preparation of Binder Solution K-2
  • a 10 mL beaker made of Teflon (registered trademark) 8 g of crosslinked homopolymer solution H-2 (0.8 g as solid content) and 1 g of crosslinked copolymer solution H-5 (0.1 g as solid content)
  • 0.1 g of pentaerythritol and 900 ⁇ L of ion-exchanged water were added and stirred until a transparent solution was obtained, thereby obtaining a binder solution K-2 having a solid content of 10 wt%.
  • Synthesis Examples 13 to 16 Preparation of binder solution K-3 to 6 Instead of 0.1 g of pentaerythritol, 1,3-propanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 1,4-butanediol (Wako Pure Chemical Industries, Ltd.) Co., Ltd.), 1,6-hexanediol (Wako Pure Chemical Industries, Ltd.) or 1,2,6-hexanetriol (Wako Pure Chemical Industries, Ltd.) was used except for 0.1 g each. In the same manner as in Example 12, binder solutions K-3 to 6 having a solid content of 10 wt% were obtained.
  • Synthesis Example 17 Preparation of binder solution K-7
  • a 10 mL beaker made of Teflon (registered trademark) 7 g of crosslinked homopolymer solution H-2 (0.7 g as solid content), 1 g of crosslinked copolymer solution H-5 (0.1 g as solid content)
  • 0.2 g of 1,4-butanediol and 1800 ⁇ L of ion-exchanged water were added and stirred until a transparent solution was obtained to obtain a binder solution K-7 having a solid content of 10 wt%.
  • Synthesis Example 18 Preparation of binder solution K-8 In a 10 mL beaker made of Teflon (registered trademark), 9 g of a crosslinked homopolymer solution H-2 (0.9 g as a solid content), 0.1 g of 1,3-propanediol and 1800 ⁇ L of ion-exchanged water were added. In addition, the mixture was stirred until a transparent solution was obtained, thereby obtaining a binder solution K-8 having a solid content of 10 wt%.
  • Synthesis Example 19 Method similar to Synthesis Example 12 except that 8 g of non-crosslinked homopolymer solution H-3 (0.8 g as solid content) was used instead of 8 g of the adjusted crosslinked homopolymer solution H-2 of binder solution K-9 As a result, a binder solution K-9 having a solid content of 10 wt% was obtained.
  • Synthesis Example 21 Preparation of Binder Solution K-11
  • Non-crosslinked homopolymer solution H-3 8 g (0.8 g as a solid content) instead of cross-linked homopolymer solution H-2 8 g
  • a binder solution K-11 having a solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12, except that 1 g of the crosslinked copolymer solution H-6 (0.1 g as the solid content) was used.
  • Synthesis Example 22 Method similar to Synthesis Example 12 except that 8 g of non-crosslinked homopolymer solution H-4 (0.8 g as solid content) was used instead of 8 g of the adjusted crosslinked homopolymer solution H-2 of binder solution K-12 As a result, a binder solution K-12 having a solid content of 10 wt% was obtained.
  • Synthesis Example 23 Preparation of Binder Solution K-13 A solid solid was prepared in the same manner as in Synthesis Example 12 except that 1 g of non-crosslinked copolymer solution H-6 (0.1 g as the solid content) was used instead of 1 g of crosslinked copolymer solution H-5. A binder solution K-13 having a content of 10 wt% was obtained.
  • Synthesis Example 24 Preparation of Binder Solution K-14
  • Non-crosslinked homopolymer solution H-4 8 g (0.8 g as a solid content) instead of 8 g of crosslinked cross-linked homopolymer solution H-2
  • a binder solution K-14 having a solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12 except that 1 g of the crosslinked copolymer solution H-6 (0.1 g as the solid content) was used.
  • Synthesis Example 25 Preparation of Binder Solution J-1 A solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12 except that 0.1 g of propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.1 g of pentaerythritol. Binder solution J-1 was obtained.
  • Synthesis Example 24 Preparation of Binder Solution J-2 A solid content of 10 wt.% was obtained in the same manner as in Synthesis Example 11 except that 0.01 g of sodium oxalate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.01 g of pentaerythritol. % Binder solution J-2 was obtained.
  • Example 1 Production of a battery using the electrode of the present invention
  • slurry composition of the present invention 8 g of silicon powder (particle size: average particle size 2.4 ⁇ m, trade name: Silgrain, manufactured by Elkem) and 1 g of acetylene black (AB) (trade name: Denka Black, Denka) (Made by Co., Ltd.) was measured and mixed for 10 minutes at a rotational speed of 2000 rpm using a rotating and rotating foam stirrer (trade name: Netsutaro Awatori, model: AR-250, manufactured by Shinky Co., Ltd.).
  • 10 g of binder solution K-1 was added and mixed for 3 hours at 2000 rpm using a rotating and rotating bubble stirrer.
  • the slurry composition is a film containing 80 wt% silicon, 10 wt% AB, and 10 wt% binder by drying after coating on the current collector.
  • the slurry composition obtained in (1) was prepared using a doctor blade (manufactured by Tester Sangyo Co., Ltd.) and a coating machine (trade name: MINI-COATER MC-20, Takara (Made by Izumi Co., Ltd.) was applied on a 20 ⁇ m thick copper foil current collector so that the Si mass of the active material was 3 mg / cm 2 . Thereafter, it was dried at 80 ° C. in air, and then dried at 150 ° C. for 12 hours under vacuum. The thickness of the film on the current collector was about 40-20 ⁇ m as measured with calipers.
  • the obtained current collector was pressed with a roll press (trade name: HSR-60150, manufactured by Hosen Co., Ltd.) to produce a lithium battery electrode having a silicon active material density of 1.4 mg / cm 3 .
  • Examples 2 to 14 Production of a battery using the electrode of the present invention A slurry composition was prepared in the same manner as in Example 1 except that 10 g of binder solution K-2 to 14 10 g was used instead of 10 g of binder solution K-1. Products, lithium battery electrodes and coin-type batteries.
  • Comparative Examples 1 and 2 Production of Battery A slurry composition for lithium batteries was prepared in the same manner as in Example 1 except that 10 g of binder solution J-1 or J-2 was used instead of 10 g of binder solution K-1. Electrodes and coin-type batteries were manufactured.
  • Comparative Example 3 Production of Battery In the same manner as in Example 1 except that 10 g of the crosslinked homopolymer solution H-2 was used instead of 10 g of the binder solution K-1, a slurry composition, an electrode for a lithium battery, and a coin-type battery Manufactured.
  • the data obtained here mainly represents the force required when the active material layer is peeled from the copper foil. Therefore, when the peel strength is strong, it means that the active material layer made of the slurry composition (here, silicon, AB and binder) is strongly bound to the copper foil of the current collector.
  • the active material layer made of the slurry composition here, silicon, AB and binder
  • Capacity retention rate (%) discharge capacity after 5 cycles / first discharge capacity ⁇ 100 The obtained results are shown in Table 2.
  • any of the batteries of Examples 1 to 14 using the electrode of the present invention showed a higher capacity retention rate than the batteries of Comparative Examples 1 to 3. This is because the homopolymer and the copolymer or the homopolymers are bonded via the alcohol according to the present invention, and are arranged evenly on the electrode and envelop the surface of the active material. This is probably because most of the active material surface was used for charging and discharging.
  • Synthesis Example 25 Synthesis of Crosslinked Homopolymer A-3
  • a 200 mL round bottom flask equipped with a stirring device, a cooling tube, a thermometer, a nitrogen introduction tube and a dropping device was added to 20 mL of methyl ethyl ketone (MEK) (manufactured by Wako Pure Chemical Industries, Ltd.).
  • MEK methyl ethyl ketone
  • Synthesis Example 26 Polymerization was carried out in the same manner as in Synthesis Example 25, except that 0.4 g of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the synthesis reaction system of crosslinked homopolymer A-4. The reaction was subjected to reaction to obtain a crosslinked homopolymer A-4.
  • 1,4-butanediol manufactured by Wako Pure Chemical Industries, Ltd.
  • Synthesis Example 27 Synthesis of Crosslinked Copolymer C-3 Instead of 4 g of acrylic acid, 2 g (28 mmol) of acrylic acid and 2 g of 2-hydroxyethyl acrylate (17 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) were used. The polymer was subjected to a polymerization reaction in the same manner as in Synthesis Example 25 to obtain a crosslinked copolymer C-3.
  • Synthesis Example 28 A polymerization reaction was performed in the same manner as in Synthesis Example 27, except that 0.4 g of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the synthesis reaction system of the crosslinked copolymer C-4. To give a crosslinked copolymer C-4.
  • Synthesis Example 29 A polymerization reaction was performed in the same manner as in Synthesis Example 27, except that 0.4 g of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the synthesis reaction system of the crosslinked copolymer C-5 .
  • Crosslinked copolymer C-5 was obtained.
  • (A) in the production of one or more polymers containing polyacrylic acid (B) when a polymerization reaction is carried out by adding a divalent to 10-valent alcohol (in other words, the polymerization reaction of the polymer and the divalent polymer
  • a divalent to 10-valent alcohol in other words, the polymerization reaction of the polymer and the divalent polymer
  • the binder composition of the present invention is subjected to a polymerization reaction and, if necessary, a neutralization treatment and / or a crosslinking reaction to produce one or more kinds of polymers containing the desired (A) polyacrylic acid. It was found that it was necessary to prepare the polymer by mixing (B) a divalent to 10-valent alcohol and (C) water.

Abstract

The purpose of the invention is to provide: an excellent binder agent composition that overcomes such problems as a reduction in charge/discharge capacity in cases of using a silicon-containing active material; a slurry composition and an electrode using said binder agent composition; and a method for preparing said electrode. This invention relates to: "a binder agent composition comprising (A) at least one type of polymer including a polyacrylic acid, (B) a bivalent to decavalent alcohol, and (C) water"; "a slurry composition for lithium batteries, comprising (1) a silicon-containing active material, (2) an electroconductive aid, and (3) said binder agent composition"; "an electrode for lithium batteries, comprising (1) a silicon-containing active material, (2) an electroconductive aid, (3) a binder agent derived from said binder agent composition, and (4) a charge collector"; and "a method for preparing an electrode for lithium batteries, characterized by applying said slurry composition on a charge collector, and then drying the same."

Description

リチウム電池用結着剤組成物Binder composition for lithium battery
　本発明は、リチウム電池において用いられる、結着剤組成物、スラリー組成物及び電極、並びに該電極の作製方法に関する。 The present invention relates to a binder composition, a slurry composition and an electrode used in a lithium battery, and a method for producing the electrode.
　リチウム電池は、二次電池として携帯電話等種々のポータブルデバイスの電源として利用されているが、近年、自動車用途等を想定した大型電池の研究開発が活発になっている。そのため、現行のリチウム電池のエネルギー密度をさらに増大させることが必要不可欠となってきている。そこで、リチウム電池の高容量化のために、活物質として炭素系材料の代わりにシリコン材料を用いることが注目されている。シリコン材料を用いたリチウム電池が高容量となる理由としては、シリコンが室温で電気化学的にリチウムと合金反応を起こすことができるため、炭素を用いた場合に比べて高い電気容量をもたらすことに起因すると考えられている。
　しかしながら、シリコンを活物質として用いた場合、充放電の際にシリコンが大きな体積変化（３倍以上に肥大化）を起こすことが知られている。そして、この体積変化により充放電時に電極構造の破壊が起き、結果として充放電容量が低下する等の問題を有していた。 Lithium batteries are used as power sources for various portable devices such as mobile phones as secondary batteries, but in recent years, research and development of large batteries that are intended for automobile applications and the like have become active. Therefore, it has become indispensable to further increase the energy density of current lithium batteries. Thus, in order to increase the capacity of the lithium battery, attention is focused on using a silicon material instead of a carbon-based material as an active material. The reason for the high capacity of lithium batteries using silicon materials is that silicon can cause an alloying reaction with lithium electrochemically at room temperature, resulting in a higher electric capacity than when carbon is used. It is thought to be caused.
However, when silicon is used as an active material, it is known that silicon undergoes a large volume change (enlarged to 3 times or more) during charge and discharge. This volume change has a problem that the electrode structure is destroyed during charge / discharge, resulting in a decrease in charge / discharge capacity.
　一方、電池の高容量化や安定性能の向上を目的として結着剤を用いる種々の試みがなされている（特許文献１、２）。しかしながら、これらの対象活物質は主に炭素材料であり、シリコンを用いた場合の上記問題の解消を目的としたものではなかった。
　また、シリコン活物質を熱硬化性の樹脂で被覆して充放電容量の低下を抑制する試みもなされている（特許文献３）が、被覆に４００℃での加熱処理が必要なことから、シリコンを活物質に用いた電極を簡便に製造できる方法ではなかった。 On the other hand, various attempts have been made to use a binder for the purpose of increasing the capacity of the battery and improving the stability performance (Patent Documents 1 and 2). However, these target active materials are mainly carbon materials, and are not intended to solve the above problems when silicon is used.
In addition, an attempt has been made to suppress a decrease in charge / discharge capacity by coating a silicon active material with a thermosetting resin (Patent Document 3). However, since the coating requires a heat treatment at 400 ° C., silicon It was not a method that can easily produce an electrode using the active material.
特開２００９－８０９７１JP2009-80971 特許４８５１０９２号Patent 4851092 特開２０１４－１９２０６４JP 2014-192064 A
　本発明は、上記の如き問題を解決する優れた結着剤組成物、それを用いたスラリー組成物及び電極、並びに該電極の作製方法の提供を課題とする。 An object of the present invention is to provide an excellent binder composition that solves the above problems, a slurry composition and an electrode using the same, and a method for producing the electrode.
　本発明者らは、活物質としてシリコンを用いた場合の上記問題を解決するために、種々の結着剤を検討してきた。その結果、ポリマー、該ポリマー同士を結合させるための２価～１０価のアルコール、及び水を含んでなる組成物を結着剤として用いることにより、シリコンを含む活物質を用いた場合であっても、優れた充放電容量が得られることを見出し、本発明を完成させた。 The present inventors have studied various binders in order to solve the above problem when silicon is used as an active material. As a result, when an active material containing silicon is used by using, as a binder, a composition comprising a polymer, a divalent to 10-valent alcohol for bonding the polymers, and water. In addition, the present inventors have found that an excellent charge / discharge capacity can be obtained and completed the present invention.
　即ち、本発明は、以下の発明［i］～［xiii］を内包する。
［i］（Ａ）ポリアクリル酸を含む１種以上のポリマー、（Ｂ）２価～１０価のアルコール、及び（Ｃ）水を含んでなる結着剤組成物。（以下、本発明の結着剤組成物と略記する場合がある。）
［ii］（Ｂ）の２価～１０価のアルコールが、下記一般式（Ｂ１）で示される化合物である、上記発明［i］記載の組成物；
Figure JPOXMLDOC01-appb-I000048
（式中、Ｒ71は、炭素数１～６のアルキレン基を表し、Ｒ72は、ヒドロキシ基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ73は、水素原子、炭素数１～６のアルキル基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ74は、－Ｏ－を鎖中に有していてもよい炭素数１～６のアルキレン基を表し、ｒは０～４の整数を表す。ただし、複数のＲ72、複数のＲ73及び複数のＲ74は、それぞれ同一であっても異なっていてもよい。）
［iii］（Ａ）が、ポリアクリル酸、及び、アクリル酸由来のモノマー単位と、下記一般式（I）又は一般式（II）で示される化合物由来のモノマー単位１～２種とを構成成分とするコポリマーである、上記発明［i］又は［ii］記載の組成物；
Figure JPOXMLDOC01-appb-I000049
［式中、Ｒ1は、水素原子又はメチル基を表し（但し、Ｒ2が水素原子の場合、Ｒ1はメチル基を表す）、Ｒ2は、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数６～１０のアリール基；炭素数７～１３のアリールアルキル基；炭素数２～９のアルコキシアルキル基；炭素数３～９のアルコキシアルコキシアルキル基；炭素数７～１３のアリールオキシアルキル基；炭素数５～７のモルホリノアルキル基；炭素数３～９のトリアルキルシリル基；酸素原子を有する又は酸素原子を有さない炭素数６～１２の脂環式炭化水素基；炭素数３～９のジアルキルアミノアルキル基；炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基；下記一般式（IV）で示される基
Figure JPOXMLDOC01-appb-I000050
（式中、Ｒ3は、ヒドロキシ基を置換基として有する又は無置換の炭素数１～６のアルキレン基を表し、Ｒ4は、水素原子、炭素数１～６のアルキル基、又はフェニル基を表し、ｖは２～２０の整数を表す。）；或いは、下記一般式（V）で示される基
Figure JPOXMLDOC01-appb-I000051
（式中、Ｒ5～Ｒ7は、それぞれ独立して炭素数１～３のアルキル基を表し、Ｒ8は、炭素数１～３のアルキレン基を表す。）を表す。］、
Figure JPOXMLDOC01-appb-I000052
（式中、Ｒ11は、水素原子又はメチル基を表し、Ｒ12は、水素原子又は炭素数１～６のアルキル基を表し、Ｒ13は、水素原子、炭素数１～６のアルキル基、炭素数３～９のジアルキルアミノアルキル基、又は炭素数１～６のヒドロキシアルキル基を表す。）。
［iv］ポリアクリル酸が、下記一般式［１］～［１３］記載の化合物及び下記一般式［１４］記載のポリマーから選ばれる架橋剤により架橋されたものである、上記発明［i］又は［ii］記載の組成物；
Figure JPOXMLDOC01-appb-I000053
（式中、ａは１～６の整数を表す。）、
Figure JPOXMLDOC01-appb-I000054
［式中、Ｒ25及びＲ26は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ21は、炭素数１～２０のアルキレン基、下記一般式［２－１］で示される基
Figure JPOXMLDOC01-appb-I000055
（式中、Ｒ22は、炭素数１～６のアルキレン基を表し、ｂは１～６の整数を表す。）、又は下記一般式［２－２］で示される基
Figure JPOXMLDOC01-appb-I000056
（式中、Ｒ23及びＲ24は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｃは１～２２の整数を表す。）を表す。］、
Figure JPOXMLDOC01-appb-I000057
（式中、Ｒ27～Ｒ33は、それぞれ独立して、炭素数１～３のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000058
（式中、Ｒ34～Ｒ37は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｄは１～６の整数を表し、ｅは０～６の整数を表し、ｆ及びｇはそれぞれ独立して０又は１の整数を表す。）、
Figure JPOXMLDOC01-appb-I000059
（式中、Ｒ38～Ｒ45は、それぞれ独立して、水素原子、ビニル基又はビニルケトン基を表し、これらの少なくとも２つ以上はビニル基又はビニルケトン基である。）、
Figure JPOXMLDOC01-appb-I000060
（式中、Ｒ46～Ｒ48は、それぞれ独立して、炭素数１～６のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000061
（式中、環Ar1は、ベンゼン環又はナフタレン環を表し、Ｒ49は、炭素数１～６のアルキレン基を表し、ｈは２～４の整数を表す。）、
Figure JPOXMLDOC01-appb-I000062
（式中、環Ar2及び環Ar3は、それぞれ独立して、ベンゼン環又はナフタレン環を表し、Ｒ50は、炭素数１～６のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000063
（式中、環Ar4は、ベンゼン環又はナフタレン環を表す。）、
Figure JPOXMLDOC01-appb-I000064
（式中、ｉは０～６の整数を表す。）、
Figure JPOXMLDOC01-appb-I000065
（式中、Ｒ51は、炭素数１～６のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000066
［式中、Ｒ52は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１２－１］で示される基
Figure JPOXMLDOC01-appb-I000067
（式中、Ｒ53は、炭素数１～６のアルキル基を表し、Ｒ54は、炭素数１～６のアルキレン基を表し、環Ar5は、ベンゼン環又はナフタレン環を表し、ｊは、０～４の整数を表す。）、或いは、下記一般式［１２－２］で示される基
Figure JPOXMLDOC01-appb-I000068
（式中、Ｒ55は、炭素数１～６のアルキレン基を表し、Ｒ53、Ｒ54、環Ar5及びｊは、上記と同じ。）を表す。］、
Figure JPOXMLDOC01-appb-I000069
［式中、Ｒ56及びＲ57は、それぞれ独立して、置換基を有する又は無置換の炭素数１～６のアルキル基、置換基を有する又は無置換の炭素数６～１０のアリール基、或いは、下記一般式［１３－１］で示される基
Figure JPOXMLDOC01-appb-I000070
（式中、Ｒ58は、炭素数１～６のアルキル基を表し、Ｒ59は、炭素数１～６のアルキレン基を表し、環Ar6は、ベンゼン環又はナフタレン環を表し、ｋは、０～５の整数を表す。）を表す。］、
Figure JPOXMLDOC01-appb-I000071
［式中、Ｒ60は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１４－１］又は［１４－２］で示される基
Figure JPOXMLDOC01-appb-I000072
（式中、Ｒ61は、炭素数１～６のアルキル基を表し、Ｒ62は、炭素数１～６のアルキレン基を表し、環Ar7は、ベンゼン環又はナフタレン環を表し、ｐは、０～４の整数を表す。）、或いは、下記一般式［１４－３］で示される基
Figure JPOXMLDOC01-appb-I000073
（式中、Ｒ63は、炭素数１～６のアルキレン基を表し、Ｒ61、Ｒ62、環Ar7及びｐは、上記と同じ。）を表し、ｍは１０～１００００の整数を表す。］。
［v］ポリアクリル酸及び／又はコポリマーが、下記一般式［１］～［１３］記載の化合物及び下記一般式［１４］記載のポリマーから選ばれる架橋剤により架橋されたものである、上記発明［iii］記載の組成物；
Figure JPOXMLDOC01-appb-I000074
（式中、ａは１～６の整数を表す。）、
Figure JPOXMLDOC01-appb-I000075
［式中、Ｒ25及びＲ26は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ21は、炭素数１～２０のアルキレン基、下記一般式［２－１］で示される基
Figure JPOXMLDOC01-appb-I000076
（式中、Ｒ22は、炭素数１～６のアルキレン基を表し、ｂは１～６の整数を表す。）、又は下記一般式［２－２］で示される基
Figure JPOXMLDOC01-appb-I000077
（式中、Ｒ23及びＲ24は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｃは１～２２の整数を表す。）を表す。］、
Figure JPOXMLDOC01-appb-I000078
（式中、Ｒ27～Ｒ33は、それぞれ独立して、炭素数１～３のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000079
（式中、Ｒ34～Ｒ37は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｄは１～６の整数を表し、ｅは０～６の整数を表し、ｆ及びｇはそれぞれ独立して０又は１の整数を表す。）、
Figure JPOXMLDOC01-appb-I000080
（式中、Ｒ38～Ｒ45は、それぞれ独立して、水素原子、ビニル基又はビニルケトン基を表し、これらの少なくとも２つ以上はビニル基又はビニルケトン基である。）、
Figure JPOXMLDOC01-appb-I000081
（式中、Ｒ46～Ｒ48は、それぞれ独立して、炭素数１～６のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000082
（式中、環Ar1は、ベンゼン環又はナフタレン環を表し、Ｒ49は、炭素数１～６のアルキレン基を表し、ｈは２～４の整数を表す。）、
Figure JPOXMLDOC01-appb-I000083
（式中、環Ar2及び環Ar3は、それぞれ独立して、ベンゼン環又はナフタレン環を表し、Ｒ50は、炭素数１～６のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000084
（式中、環Ar4は、ベンゼン環又はナフタレン環を表す。）、
Figure JPOXMLDOC01-appb-I000085
（式中、ｉは０～６の整数を表す。）、
Figure JPOXMLDOC01-appb-I000086
（式中、Ｒ51は、炭素数１～６のアルキレン基を表す。）、
Figure JPOXMLDOC01-appb-I000087
［式中、Ｒ52は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１２－１］で示される基
Figure JPOXMLDOC01-appb-I000088
（式中、Ｒ53は、炭素数１～６のアルキル基を表し、Ｒ54は、炭素数１～６のアルキレン基を表し、環Ar5は、ベンゼン環又はナフタレン環を表し、ｊは、０～４の整数を表す。）、或いは、下記一般式［１２－２］で示される基
Figure JPOXMLDOC01-appb-I000089
（式中、Ｒ55は、炭素数１～６のアルキレン基を表し、Ｒ53、Ｒ54、環Ar5及びｊは、上記と同じ。）を表す。］、
Figure JPOXMLDOC01-appb-I000090
［式中、Ｒ56及びＲ57は、それぞれ独立して、置換基を有する又は無置換の炭素数１～６のアルキル基、置換基を有する又は無置換の炭素数６～１０のアリール基、或いは、下記一般式［１３－１］で示される基
Figure JPOXMLDOC01-appb-I000091
（式中、Ｒ58は、炭素数１～６のアルキル基を表し、Ｒ59は、炭素数１～６のアルキレン基を表し、環Ar6は、ベンゼン環又はナフタレン環を表し、ｋは、０～５の整数を表す。）を表す。］、
Figure JPOXMLDOC01-appb-I000092
［式中、Ｒ60は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１４－１］又は［１４－２］で示される基
Figure JPOXMLDOC01-appb-I000093
（式中、Ｒ61は、炭素数１～６のアルキル基を表し、Ｒ62は、炭素数１～６のアルキレン基を表し、環Ar7は、ベンゼン環又はナフタレン環を表し、ｐは、０～４の整数を表す。）、或いは、下記一般式［１４－３］で示される基
Figure JPOXMLDOC01-appb-I000094
（式中、Ｒ63は、炭素数１～６のアルキレン基を表し、Ｒ61、Ｒ62、環Ar7及びｐは、上記と同じ。）を表し、ｍは１０～１００００の整数を表す。］。
［vi］ポリアクリル酸及びコポリマーが、一般式［１］～［１３］記載の化合物及び一般式［１４］記載のポリマーから選ばれる架橋剤により架橋されたものである、上記発明［v］記載の組成物。
［vii］１）シリコンを含有する活物質、２）導電助剤、及び３）上記発明［i］～［vi］の何れかに記載の結着剤組成物を含んでなるリチウム電池用のスラリー組成物。（以下、本発明のスラリー組成物と略記する場合がある。）
［viii］シリコンを含有する活物質が、シリコン；シリコン酸化物；金属と結合したシリコン；或いは、炭素、シリコン、シリコン酸化物又は金属と結合したシリコンのうち少なくとも２種以上を混合したものを含有する、上記発明［vii］記載の組成物。
［ix］負極作製用である、上記発明［vii］又は［viii］記載の組成物。
［x］１）シリコンを含有する活物質、２）導電助剤、３）上記発明［i］～［vi］の何れかに記載の結着剤組成物由来の結着剤、及び４）集電体を有するリチウム電池用の電極。（以下、本発明の電極と略記する場合がある。）
［xi］シリコンを含有する活物質が、シリコン；シリコン酸化物；金属と結合したシリコン；或いは、炭素、シリコン、シリコン酸化物又は金属と結合したシリコンのうち少なくとも２種以上を混合したものを含有する、上記発明［x］記載の電極。
［xii］電極が負極である、上記発明［x］又は［xi］記載の電極。
［xiii］上記発明［vii］～［ix］の何れかに記載のスラリー組成物を集電体上に塗布した後、乾燥させることを特徴とする、リチウム電池用の電極作製方法。 That is, the present invention includes the following inventions [i] to [xiii].
[I] A binder composition comprising (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water. (Hereinafter, it may be abbreviated as the binder composition of the present invention.)
[Ii] The composition according to the above-mentioned invention [i], wherein the divalent to 10-valent alcohol of (B) is a compound represented by the following general formula (B1);
Figure JPOXMLDOC01-appb-I000048
Wherein R 71 represents an alkylene group having 1 to 6 carbon atoms, R 72 represents a hydroxy group or a hydroxyalkyl group having 1 to 6 carbon atoms, R 73 represents a hydrogen atom, 1 to 6 carbon atoms Or an alkyl group having 1 to 6 carbon atoms, R 74 represents an alkylene group having 1 to 6 carbon atoms which may have —O— in the chain, and r represents 0 to 4 carbon atoms. Represents an integer, provided that the plurality of R 72 , the plurality of R 73 and the plurality of R 74 may be the same or different.
[Iii] (A) comprises polyacrylic acid and a monomer unit derived from acrylic acid and one or two monomer units derived from a compound represented by the following general formula (I) or general formula (II) A composition according to the above-mentioned invention [i] or [ii],
Figure JPOXMLDOC01-appb-I000049
[Wherein R 1 represents a hydrogen atom or a methyl group (provided that when R 2 is a hydrogen atom, R 1 represents a methyl group), R 2 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an aryl group having 6 to 10 carbon atoms; an arylalkyl group having 7 to 13 carbon atoms; an alkoxyalkyl group having 2 to 9 carbon atoms; An alkoxyalkoxyalkyl group having 3 to 9 carbon atoms; an aryloxyalkyl group having 7 to 13 carbon atoms; a morpholinoalkyl group having 5 to 7 carbon atoms; a trialkylsilyl group having 3 to 9 carbon atoms; having an oxygen atom or having an oxygen atom An alicyclic hydrocarbon group having 6 to 12 carbon atoms; a dialkylaminoalkyl group having 3 to 9 carbon atoms; a hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms; represented by the following general formula (IV) Base
Figure JPOXMLDOC01-appb-I000050
(Wherein R 3 represents a hydroxyl group as a substituent or an unsubstituted alkylene group having 1 to 6 carbon atoms, and R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. V represents an integer of 2 to 20); or a group represented by the following general formula (V)
Figure JPOXMLDOC01-appb-I000051
(Wherein R 5 to R 7 each independently represents an alkyl group having 1 to 3 carbon atoms, and R 8 represents an alkylene group having 1 to 3 carbon atoms). ],
Figure JPOXMLDOC01-appb-I000052
(Wherein R 11 represents a hydrogen atom or a methyl group, R 12 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents a dialkylaminoalkyl group having 3 to 9 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.)
[Iv] The above-mentioned invention [i], wherein the polyacrylic acid is crosslinked with a crosslinking agent selected from a compound represented by the following general formulas [1] to [13] and a polymer represented by the following general formula [14] [Ii] The composition according to
Figure JPOXMLDOC01-appb-I000053
(Wherein, a represents an integer of 1 to 6),
Figure JPOXMLDOC01-appb-I000054
[Wherein R 25 and R 26 each independently represent a hydrogen atom or a methyl group, R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1]
Figure JPOXMLDOC01-appb-I000055
(Wherein R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6), or a group represented by the following general formula [2-2]
Figure JPOXMLDOC01-appb-I000056
(Wherein R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22). ],
Figure JPOXMLDOC01-appb-I000057
(Wherein R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms),
Figure JPOXMLDOC01-appb-I000058
(Wherein R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms, d represents an integer of 1 to 6, e represents an integer of 0 to 6, f and g Each independently represents an integer of 0 or 1.)
Figure JPOXMLDOC01-appb-I000059
(Wherein R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group).
Figure JPOXMLDOC01-appb-I000060
(Wherein R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms),
Figure JPOXMLDOC01-appb-I000061
(In the formula, ring Ar 1 represents a benzene ring or a naphthalene ring, R 49 represents an alkylene group having 1 to 6 carbon atoms, and h represents an integer of 2 to 4).
Figure JPOXMLDOC01-appb-I000062
(In the formula, each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring, and R 50 represents an alkylene group having 1 to 6 carbon atoms).
Figure JPOXMLDOC01-appb-I000063
(Wherein the ring Ar 4 represents a benzene ring or a naphthalene ring),
Figure JPOXMLDOC01-appb-I000064
(Wherein i represents an integer of 0 to 6),
Figure JPOXMLDOC01-appb-I000065
(Wherein R 51 represents an alkylene group having 1 to 6 carbon atoms),
Figure JPOXMLDOC01-appb-I000066
[Wherein R 52 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [12-1] Group represented by
Figure JPOXMLDOC01-appb-I000067
(Wherein R 53 represents an alkyl group having 1 to 6 carbon atoms, R 54 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 5 represents a benzene ring or a naphthalene ring, j is Represents an integer of 0 to 4, or a group represented by the following general formula [12-2]
Figure JPOXMLDOC01-appb-I000068
(Wherein R 55 represents an alkylene group having 1 to 6 carbon atoms, and R 53 , R 54 , and rings Ar 5 and j are the same as above). ],
Figure JPOXMLDOC01-appb-I000069
[Wherein, R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1]
Figure JPOXMLDOC01-appb-I000070
(Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5). ],
Figure JPOXMLDOC01-appb-I000071
[Wherein R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2]
Figure JPOXMLDOC01-appb-I000072
(Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3]
Figure JPOXMLDOC01-appb-I000073
(Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000. ].
[V] The above invention, wherein the polyacrylic acid and / or copolymer is crosslinked with a crosslinking agent selected from the compounds represented by the following general formulas [1] to [13] and the polymer represented by the following general formula [14]: [Iii] a composition according to the description;
Figure JPOXMLDOC01-appb-I000074
(Wherein, a represents an integer of 1 to 6),
Figure JPOXMLDOC01-appb-I000075
[Wherein R 25 and R 26 each independently represent a hydrogen atom or a methyl group, R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1]
Figure JPOXMLDOC01-appb-I000076
(Wherein R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6), or a group represented by the following general formula [2-2]
Figure JPOXMLDOC01-appb-I000077
(Wherein R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22). ],
Figure JPOXMLDOC01-appb-I000078
(Wherein R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms),
Figure JPOXMLDOC01-appb-I000079
(Wherein R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms, d represents an integer of 1 to 6, e represents an integer of 0 to 6, f and g Each independently represents an integer of 0 or 1.)
Figure JPOXMLDOC01-appb-I000080
(Wherein R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group).
Figure JPOXMLDOC01-appb-I000081
(Wherein R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms),
Figure JPOXMLDOC01-appb-I000082
(In the formula, ring Ar 1 represents a benzene ring or a naphthalene ring, R 49 represents an alkylene group having 1 to 6 carbon atoms, and h represents an integer of 2 to 4).
Figure JPOXMLDOC01-appb-I000083
(In the formula, each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring, and R 50 represents an alkylene group having 1 to 6 carbon atoms).
Figure JPOXMLDOC01-appb-I000084
(Wherein the ring Ar 4 represents a benzene ring or a naphthalene ring),
Figure JPOXMLDOC01-appb-I000085
(Wherein i represents an integer of 0 to 6),
Figure JPOXMLDOC01-appb-I000086
(Wherein R 51 represents an alkylene group having 1 to 6 carbon atoms),
Figure JPOXMLDOC01-appb-I000087
[Wherein R 52 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [12-1] Group represented by
Figure JPOXMLDOC01-appb-I000088
(Wherein R 53 represents an alkyl group having 1 to 6 carbon atoms, R 54 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 5 represents a benzene ring or a naphthalene ring, j is Represents an integer of 0 to 4, or a group represented by the following general formula [12-2]
Figure JPOXMLDOC01-appb-I000089
(Wherein R 55 represents an alkylene group having 1 to 6 carbon atoms, and R 53 , R 54 , and rings Ar 5 and j are the same as above). ],
Figure JPOXMLDOC01-appb-I000090
[Wherein, R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1]
Figure JPOXMLDOC01-appb-I000091
(Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5). ],
Figure JPOXMLDOC01-appb-I000092
[Wherein R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2]
Figure JPOXMLDOC01-appb-I000093
(Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3]
Figure JPOXMLDOC01-appb-I000094
(Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000. ].
[Vi] The above invention [v], wherein the polyacrylic acid and the copolymer are crosslinked with a crosslinking agent selected from the compounds represented by the general formulas [1] to [13] and the polymer represented by the general formula [14]. Composition.
[Vii] 1) an active material containing silicon, 2) a conductive additive, and 3) a slurry for a lithium battery comprising the binder composition according to any one of the above inventions [i] to [vi] Composition. (Hereinafter, it may be abbreviated as the slurry composition of the present invention.)
[Viii] The active material containing silicon contains silicon, silicon oxide, silicon bonded to metal, or a mixture of carbon, silicon, silicon oxide, or silicon bonded to metal, at least two kinds A composition according to the invention [vii].
[Ix] The composition according to the above-mentioned invention [vii] or [viii], which is for producing a negative electrode.
[X] 1) an active material containing silicon, 2) a conductive auxiliary agent, 3) a binder derived from the binder composition according to any one of the above inventions [i] to [vi], and 4) a collector An electrode for a lithium battery having an electric body. (Hereafter, it may be abbreviated as the electrode of the present invention.)
[Xi] Active material containing silicon includes silicon, silicon oxide, silicon bonded to metal, or a mixture of at least two of carbon, silicon, silicon oxide, or silicon bonded to metal An electrode according to the invention [x].
[Xii] The electrode according to the above-mentioned invention [x] or [xi], wherein the electrode is a negative electrode.
[Xiii] A method for producing an electrode for a lithium battery, wherein the slurry composition according to any one of the above inventions [vii] to [ix] is applied on a current collector and then dried.
　本発明の結着剤組成物を用いてリチウム電極を作製することにより、シリコンを含む活物質を用いた場合であっても高い充放電容量を維持する電極の提供を可能とする。また、該電極を用いることにより、長期にわたり高容量を保持し得る電池の提供を可能とする。 By producing a lithium electrode using the binder composition of the present invention, it is possible to provide an electrode that maintains a high charge / discharge capacity even when an active material containing silicon is used. Further, by using the electrode, it is possible to provide a battery that can maintain a high capacity for a long period of time.
　本明細書において、バインダー溶液とは、１種以上のポリマーとその他の化合物（架橋剤等の添加剤）とを水に混合させてなる水溶液を示す用語であり、バインダーとは、該バインダー溶液を乾燥させ水分を除去した状態を示す用語である。本発明の結着剤組成物はバインダー溶液の一種であり、本発明の結着剤組成物由来の結着剤はバインダーの一種である。 In this specification, the binder solution is a term indicating an aqueous solution in which one or more kinds of polymers and other compounds (additives such as a crosslinking agent) are mixed with water, and the binder refers to the binder solution. It is a term that indicates a state in which moisture has been removed by drying. The binder composition of the present invention is a kind of binder solution, and the binder derived from the binder composition of the present invention is a kind of binder.
　本明細書において、（メタ）アクリル酸とは、アクリル酸、メタクリル酸及びそれらの混合物を総称する用語であり、他の類似の表現についても同様である。 In the present specification, (meth) acrylic acid is a generic term for acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.
　また、本明細書において、n-はnormal-体を、i-はiso-体を、それぞれ表す。 In the present specification, n- represents normal-form and i- represents iso-form.
［（Ａ）ポリアクリル酸を含む１種以上のポリマー］
　本発明の結着剤組成物は、少なくともポリアクリル酸を含み、要すればポリアクリル酸以外のポリマーを含むものである。本明細書において、（Ａ）ポリアクリル酸を含む１種以上のポリマーとは、（Ａ１）ポリアクリル酸のみ、又は（Ａ２）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群を意味する。 [(A) One or More Polymers Containing Polyacrylic Acid]
The binder composition of the present invention contains at least polyacrylic acid and, if necessary, a polymer other than polyacrylic acid. In the present specification, (A) one or more kinds of polymers containing polyacrylic acid means (A1) only polyacrylic acid, or (A2) a polymer composed of a polymer other than polyacrylic acid and one or more kinds of polyacrylic acid. Means group.
　上記ポリアクリル酸以外のポリマーとしては、通常この分野で用いられる従来公知のポリマーであればよく、ホモポリマーであってもコポリマーであってもよい。また、ポリアクリル酸以外のポリマーは、１種のみであっても２種以上であってもよく、１種のみが好ましい。このようなポリマーとしては、カルボキシ基を有するモノマー単位を構成成分に含むポリマーが好ましく、カルボキシ基を有するモノマー単位を構成成分に含むコポリマーがより好ましく、アクリル酸由来のモノマー単位を構成成分に含むコポリマーがさらに好ましい。 The polymer other than the polyacrylic acid may be a conventionally known polymer that is usually used in this field, and may be a homopolymer or a copolymer. In addition, the polymer other than polyacrylic acid may be one type or two or more types, and only one type is preferable. As such a polymer, a polymer including a monomer unit having a carboxy group as a constituent component is preferable, a copolymer including a monomer unit having a carboxy group as a constituent component is more preferable, and a copolymer including a monomer unit derived from acrylic acid as a constituent component Is more preferable.
　アクリル酸由来のモノマー単位を構成成分に含むコポリマーとしては、具体的には例えば、アクリル酸由来のモノマー単位と、下記一般式（I）又は一般式（II）で示される化合物由来のモノマー単位１～２種とを構成成分とするコポリマー（以下、本発明に係るコポリマーと略記する場合がある）が挙げられる。 Specific examples of the copolymer containing a monomer unit derived from acrylic acid as a constituent component include, for example, a monomer unit derived from acrylic acid and a monomer unit 1 derived from a compound represented by the following general formula (I) or general formula (II). Copolymers having two or more components as constituents (hereinafter sometimes abbreviated as copolymers according to the present invention) can be mentioned.
Figure JPOXMLDOC01-appb-I000095
（式中、Ｒ1及びＲ2は、上記と同じ。）
Figure JPOXMLDOC01-appb-I000095
(In the formula, R 1 and R 2 are the same as above.)
Figure JPOXMLDOC01-appb-I000096
（式中、Ｒ11～Ｒ13は、上記と同じ。）
Figure JPOXMLDOC01-appb-I000096
(Wherein R 11 to R 13 are the same as above)
　一般式（I）のＲ2における炭素数１～２０のアルキル基としては、炭素数１～１０のものが好ましく、炭素数１～６のものがより好ましい。また、直鎖状、分枝状及び環状のうちいずれであってもよく、直鎖状が好ましい。具体的には例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、シクロブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1,2-ジメチルプロピル基、シクロペンチル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、1,2-ジメチルブチル基、2,3-ジメチルブチル基、シクロヘキシル基、n-ヘプチル基、イソヘプチル基、sec-ヘプチル基、tert-ヘプチル基、ネオヘプチル基、シクロヘプチル基、n-オクチル基、イソオクチル基、sec-オクチル基、tert-オクチル基、ネオオクチル基、シクロオクチル基、n-ノニル基、イソノニル基、sec-ノニル基、tert-ノニル基、ネオノニル基、シクロノニル基、n-デシル基、イソデシル基、sec-デシル基、tert-デシル基、ネオデシル基、シクロデシル基、n-ウンデシル基、n-ドデシル基、n-トリデシル基、n-テトラデシル基、n-ペンタデシル基、n-ヘキサデシル基、n-ヘプタデシル基、n-オクタデシル基、n-ノナデシル基、n-イコシル基等が挙げられ、中でもメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1,2-ジメチルプロピル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、1,2-ジメチルブチル基、2,3-ジメチルブチル基が好ましく、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基がより好ましく、n-ブチル基、n-ペンチル基、n-ヘキシル基が特に好ましい。 The alkyl group having 1 to 20 carbon atoms in R 2 of the general formula (I) preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec -Pentyl, tert-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, 2 -Methylpentyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl, cycloheptyl, n -Octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neono Group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, Examples include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, among them methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group N-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group are preferred, methyl group, ethyl Group, n- Propyl group, n- butyl group, n- pentyl group, more preferably n- hexyl, n- butyl, n- pentyl, n- hexyl group are particularly preferred.
　一般式（I）のＲ2におけるフッ素原子で置換された炭素数１～２０のアルキル基としては、末端部分がフッ素化されたものが好ましく、パーフルオロアルキル基又は(パーフルオロアルキル)アルキル基が好ましく、(パーフルオロアルキル)アルキル基がより好ましい。また、炭素数１～１０のものが好ましく、直鎖状が好ましい。具体的には例えば、フルオロエチル基、フルオロプロピル基、フルオロブチル基、フルオロペンチル基、フルオロヘキシル基、フルオロヘプチル基、フルオロオクチル基、フルオロノニル基、フルオロデシル基、フルオロウンデシル基、フルオロドデシル基、フルオロトリデシル基、フルオロテトラデシル基、フルオロペンタデシル基、フルオロヘキサデシル基、フルオロヘプタデシル基、フルオロオクタデシル基、フルオロノナデシル基、フルオロイコシル基、トリフルオロメチル基、トリフルオロエチル基、トリフルオロプロピル基、トリフルオロブチル基、トリフルオロペンチル基、トリフルオロヘキシル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロペンチル基、パーフルオロヘキシル基、(パーフルオロブチル)メチル基、(パーフルオロブチル)エチル基、(パーフルオロブチル)プロピル基、(パーフルオロヘキシル)メチル基、(パーフルオロヘキシル)エチル基、(パーフルオロヘキシル)プロピル基等が挙げられ、中でもトリフルオロメチル基、トリフルオロエチル基、トリフルオロプロピル基、トリフルオロブチル基、トリフルオロペンチル基、トリフルオロヘキシル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロペンチル基、パーフルオロヘキシル基、(パーフルオロブチル)メチル基、(パーフルオロブチル)エチル基、(パーフルオロブチル)プロピル基、(パーフルオロヘキシル)メチル基、(パーフルオロヘキシル)エチル基、(パーフルオロヘキシル)プロピル基が好ましく、トリフルオロメチル基、トリフルオロエチル基、(パーフルオロブチル)メチル基、(パーフルオロブチル)エチル基、(パーフルオロヘキシル)メチル基、(パーフルオロヘキシル)エチル基がより好ましく、(パーフルオロブチル)エチル基、(パーフルオロヘキシル)エチル基が特に好ましい。 As the alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom in R 2 of the general formula (I), those having a terminal portion fluorinated are preferred, and a perfluoroalkyl group or a (perfluoroalkyl) alkyl group is Preferably, a (perfluoroalkyl) alkyl group is more preferable. Further, those having 1 to 10 carbon atoms are preferable, and a straight chain is preferable. Specifically, for example, fluoroethyl group, fluoropropyl group, fluorobutyl group, fluoropentyl group, fluorohexyl group, fluoroheptyl group, fluorooctyl group, fluorononyl group, fluorodecyl group, fluoroundecyl group, fluorododecyl group , Fluorotridecyl group, fluorotetradecyl group, fluoropentadecyl group, fluorohexadecyl group, fluoroheptadecyl group, fluorooctadecyl group, fluorononadecyl group, fluoroicosyl group, trifluoromethyl group, trifluoroethyl group, Trifluoropropyl group, trifluorobutyl group, trifluoropentyl group, trifluorohexyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl (Perfluorobutyl) methyl group, (perfluorobutyl) ethyl group, (perfluorobutyl) propyl group, (perfluorohexyl) methyl group, (perfluorohexyl) ethyl group, (perfluorohexyl) propyl group, etc. Among them, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, trifluorobutyl group, trifluoropentyl group, trifluorohexyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorobutyl group, Fluoropentyl group, perfluorohexyl group, (perfluorobutyl) methyl group, (perfluorobutyl) ethyl group, (perfluorobutyl) propyl group, (perfluorohexyl) methyl group, (perfluorohexyl) ethyl group, Perfluorohexyl) propyl group is preferred, R-methyl group, trifluoroethyl group, (perfluorobutyl) methyl group, (perfluorobutyl) ethyl group, (perfluorohexyl) methyl group, (perfluorohexyl) ethyl group are more preferable, (perfluorobutyl) ethyl group The (perfluorohexyl) ethyl group is particularly preferred.
　一般式（I）のＲ2におけるヒドロキシ基で置換された炭素数１～２０のアルキル基としては、末端部分がヒドロキシ基で置換されたものが好ましく、１～２個の水素がヒドロキシ基で置換されたものが好ましく、１個の水素がヒドロキシ基で置換されたものがより好ましい。また、炭素数１～６のものが好ましく、直鎖状が好ましい。具体的には例えば、ヒドロキシメチル基、ヒドロキシエチル基、ジヒドロキシエチル基、ヒドロキシプロピル基、ジヒドロキシプロピル基、ヒドロキシブチル基、ジヒドロキシブチル基、ヒドロキシペンチル基、ジヒドロキシペンチル基、ヒドロキシヘキシル基、ジヒドロキシヘキシル基、ヒドロキシヘプチル基、ヒドロキシオクチル基、ヒドロキシノニル基、ヒドロキシデシル基、ヒドロキシウンデシル基、ヒドロキシドデシル基、ヒドロキシトリデシル基、ヒドロキシテトラデシル基、ヒドロキシペンタデシル基、ヒドロキシヘキサデシル基、ヒドロキシヘプタデシル基、ヒドロキシオクタデシル基、ヒドロキシノナデシル基、ヒドロキシイコシル基等が挙げられ、中でもヒドロキシメチル基、ヒドロキシエチル基、ジヒドロキシエチル基、ヒドロキシプロピル基、ジヒドロキシプロピル基、ヒドロキシブチル基、ジヒドロキシブチル基、ヒドロキシペンチル基、ジヒドロキシペンチル基、ヒドロキシヘキシル基、ジヒドロキシヘキシル基が好ましく、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシヘキシル基がより好ましく、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基がさらに好ましく、ヒドロキシエチル基が特に好ましい。 As the alkyl group having 1 to 20 carbon atoms substituted with a hydroxy group in R 2 of the general formula (I), those having a terminal portion substituted with a hydroxy group are preferable, and 1 to 2 hydrogen atoms are substituted with a hydroxy group. Those in which one hydrogen is replaced with a hydroxy group are more preferable. Further, those having 1 to 6 carbon atoms are preferred, and a straight chain is preferred. Specifically, for example, hydroxymethyl group, hydroxyethyl group, dihydroxyethyl group, hydroxypropyl group, dihydroxypropyl group, hydroxybutyl group, dihydroxybutyl group, hydroxypentyl group, dihydroxypentyl group, hydroxyhexyl group, dihydroxyhexyl group, Hydroxyheptyl group, hydroxyoctyl group, hydroxynonyl group, hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group, hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, hydroxyheptadecyl group, Examples include hydroxyoctadecyl group, hydroxynonadecyl group, hydroxyicosyl group, etc., among which hydroxymethyl group, hydroxyethyl group, dihydroxyethyl , Hydroxypropyl group, dihydroxypropyl group, hydroxybutyl group, dihydroxybutyl group, hydroxypentyl group, dihydroxypentyl group, hydroxyhexyl group, dihydroxyhexyl group are preferred, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group Hydroxypentyl group and hydroxyhexyl group are more preferable, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group and hydroxybutyl group are more preferable, and hydroxyethyl group is particularly preferable.
　一般式（I）のＲ2における炭素数６～１０のアリール基としては、フェニル基、ナフチル基等が挙げられ、フェニル基が好ましい。 Examples of the aryl group having 6 to 10 carbon atoms in R 2 of the general formula (I) include a phenyl group and a naphthyl group, and a phenyl group is preferable.
　一般式（I）のＲ2における炭素数７～１３のアリールアルキル基としては、炭素数７～９のものが好ましい。具体的には例えば、ベンジル基、フェニルエチル基、フェニルプロピル基、ナフチルメチル基、ナフチルエチル基、ナフチルプロピル基等が挙げられ、中でもベンジル基、フェニルエチル基、フェニルプロピル基が好ましく、ベンジル基がより好ましい。 The arylalkyl group having 7 to 13 carbon atoms in R 2 of the general formula (I) is preferably one having 7 to 9 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, etc. Among them, a benzyl group, a phenylethyl group, and a phenylpropyl group are preferable, and a benzyl group is preferable. More preferred.
　一般式（I）のＲ2における炭素数２～９のアルコキシアルキル基としては、メトキシメチル基、メトキシエチル基、メトキシプロピル基、メトキシブチル基、メトキシペンチル基、メトキシヘキシル基、メトキシヘプチル基、メトキシオクチル基、エトキシメチル基、エトキシエチル基、エトキシプロピル基、エトキシブチル基、エトキシペンチル基、エトキシヘキシル基、エトキシヘプチル基、プロポキシメチル基、プロポキシエチル基、プロポキシプロピル基、プロポキシブチル基、プロポキシペンチル基、プロポキシヘキシル基等が挙げられる。 Examples of the alkoxyalkyl group having 2 to 9 carbon atoms in R 2 of the general formula (I) include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, methoxyhexyl group, methoxyheptyl group, methoxy Octyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, ethoxypentyl group, ethoxyhexyl group, ethoxyheptyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, propoxybutyl group, propoxypentyl group And propoxyhexyl group.
　一般式（I）のＲ2における炭素数３～９のアルコキシアルコキシアルキル基としては、メトキシメトキシメチル基、メトキシメトキシエチル基、メトキシメトキシプロピル基、エトキシメトキシメチル基、エトキシメトキシエチル基、エトキシメトキシプロピル基、プロポキシメトキシメチル基、プロポキシメトキシエチル基、プロポキシメトキシプロピル基、メトキシエトキシメチル基、メトキシエトキシエチル基、メトキシエトキシプロピル基、エトキシエトキシメチル基、エトキシエトキシエチル基、エトキシエトキシプロピル基、プロポキシエトキシメチル基、プロポキシエトキシエチル基、プロポキシエトキシプロピル基、メトキシプロポキシメチル基、メトキシプロポキシエチル基、メトキシプロポキシプロピル基、エトキシプロポキシメチル基、エトキシプロポキシエチル基、エトキシプロポキシプロピル基、プロポキシプロポキシメチル基、プロポキシプロポキシエチル基、プロポキシプロポキシプロピル基等が挙げられる。 Examples of the alkoxyalkoxyalkyl group having 3 to 9 carbon atoms in R 2 of the general formula (I) include a methoxymethoxymethyl group, a methoxymethoxyethyl group, a methoxymethoxypropyl group, an ethoxymethoxymethyl group, an ethoxymethoxyethyl group, and an ethoxymethoxypropyl group. Group, propoxymethoxymethyl group, propoxymethoxyethyl group, propoxymethoxypropyl group, methoxyethoxymethyl group, methoxyethoxyethyl group, methoxyethoxypropyl group, ethoxyethoxymethyl group, ethoxyethoxyethyl group, ethoxyethoxypropyl group, propoxyethoxymethyl Group, propoxyethoxyethyl group, propoxyethoxypropyl group, methoxypropoxymethyl group, methoxypropoxyethyl group, methoxypropoxypropyl group, ethoxy group Pokishimechiru group, ethoxypropoxy ethyl, ethoxy propoxy propyl group, propoxymethyl propoxymethyl group, propoxy propoxy ethyl group, etc. propoxy propoxy propyl group.
　一般式（I）のＲ2における炭素数７～１３のアリールオキシアルキル基としては、炭素数７～９のものが好ましい。具体的には例えば、フェノキシメチル基、フェノキシエチル基、フェノキシプロピル基、ナフチルオキシメチル基、ナフチルオキシエチル基、ナフチルオキシプロピル基等が挙げられ、中でもフェノキシメチル基、フェノキシエチル基、フェノキシプロピル基が好ましく、フェノキシエチル基がより好ましい。 The aryloxyalkyl group having 7 to 13 carbon atoms in R 2 of the general formula (I) is preferably one having 7 to 9 carbon atoms. Specific examples include a phenoxymethyl group, a phenoxyethyl group, a phenoxypropyl group, a naphthyloxymethyl group, a naphthyloxyethyl group, a naphthyloxypropyl group, and the like, among which a phenoxymethyl group, a phenoxyethyl group, and a phenoxypropyl group are mentioned. Preferably, a phenoxyethyl group is more preferable.
　一般式（I）のＲ2における炭素数５～７のモルホリノアルキル基としては、例えばモルホリノメチル基、モルホリノエチル基、モルホリノプロピル基等が挙げられる。 Examples of the morpholinoalkyl group having 5 to 7 carbon atoms in R 2 of the general formula (I) include a morpholinomethyl group, a morpholinoethyl group, a morpholinopropyl group, and the like.
　一般式（I）のＲ2における炭素数３～９のトリアルキルシリル基としては、例えばトリメチルシリル基、トリエチルシリル基、トリプロピルシリル基、ジメチルエチルシリル基、ジエチルメチルシリル基等が挙げられる。 Examples of the trialkylsilyl group having 3 to 9 carbon atoms in R 2 of the general formula (I) include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group and the like.
　一般式（I）のＲ2における酸素原子を有する炭素数６～１２の脂環式炭化水素基としては、ジシクロペンテニルオキシエチル基等が挙げられる。 Examples of the alicyclic hydrocarbon group having 6 to 12 carbon atoms having an oxygen atom in R 2 of the general formula (I) include a dicyclopentenyloxyethyl group.
　一般式（I）のＲ2における酸素原子を有さない炭素数６～１２の脂環式炭化水素基としては、シクロヘキシル基、イソボルニル基、ジシクロペンタニル基等が挙げられる。 Examples of the alicyclic hydrocarbon group having 6 to 12 carbon atoms and having no oxygen atom in R 2 of the general formula (I) include a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.
　一般式（I）のＲ2における炭素数３～９のジアルキルアミノアルキル基としては、ジメチルアミノメチル基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジエチルアミノメチル基、ジエチルアミノエチル基、ジエチルアミノプロピル基、ジプロピルアミノメチル基、ジプロピルアミノエチル基、ジプロピルアミノプロピル基等が挙げられる。 Examples of the dialkylaminoalkyl group having 3 to 9 carbon atoms in R 2 of the general formula (I) include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, A propylaminomethyl group, a dipropylaminoethyl group, a dipropylaminopropyl group, etc. are mentioned.
　一般式（I）のＲ2における炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基のアルキル基は通常炭素数１～６であり、炭素数１～３のものが好ましく、直鎖状のものが好ましい。炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基としては、具体的には例えば、2-ヘキサヒドロフタルイミドメチル基、2-ヘキサヒドロフタルイミドエチル基、2-ヘキサヒドロフタルイミドプロピル基、2-ヘキサヒドロフタルイミドブチル基、2-ヘキサヒドロフタルイミドペンチル基、2-ヘキサヒドロフタルイミドヘキシル基等が挙げられる。 The alkyl group of the hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms in R 2 of the general formula (I) usually has 1 to 6 carbon atoms, preferably one having 1 to 3 carbon atoms, Those are preferred. Specific examples of the hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms include 2-hexahydrophthalimidomethyl group, 2-hexahydrophthalimidoethyl group, 2-hexahydrophthalimidopropyl group, and 2-hexahydrophthalimido group. Examples thereof include hydrophthalimidobutyl group, 2-hexahydrophthalimidopentyl group, and 2-hexahydrophthalimidohexyl group.
　一般式（IV）のＲ3におけるヒドロキシ基を置換基として有する炭素数１～６のアルキレン基としては、１個の水素がヒドロキシ基で置換されたものが好ましく、炭素数１～３のものが好ましい。具体的には例えば、ヒドロキシメチレン基、ヒドロキシエチレン基、ヒドロキシトリメチレン基、ヒドロキシテトラメチレン基、ヒドロキシペンタメチレン基、ヒドロキシヘキサメチレン基等が挙げられ、中でもヒドロキシメチレン基、ヒドロキシエチレン基、ヒドロキシトリメチレン基が好ましく、ヒドロキシトリメチレン基がより好ましい。 As the alkylene group having 1 to 6 carbon atoms having a hydroxy group as a substituent in R 3 of the general formula (IV), one in which one hydrogen is substituted with a hydroxy group is preferable, and one having 1 to 3 carbon atoms is preferred. preferable. Specific examples include a hydroxymethylene group, a hydroxyethylene group, a hydroxytrimethylene group, a hydroxytetramethylene group, a hydroxypentamethylene group, and a hydroxyhexamethylene group. Among them, a hydroxymethylene group, a hydroxyethylene group, a hydroxytrimethylene group, and the like can be given. Group is preferred, and hydroxytrimethylene group is more preferred.
　一般式（IV）のＲ3における無置換の炭素数１～６のアルキレン基としては、炭素数２～４のものが好ましい。具体的には例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が挙げられ、中でもエチレン基、トリメチレン基、プロピレン基、テトラメチレン基が好ましく、エチレン基、プロピレン基がより好ましく、エチレン基が特に好ましい。 The unsubstituted alkylene group having 1 to 6 carbon atoms in R 3 of the general formula (IV) is preferably one having 2 to 4 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., among which an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group are preferable, An ethylene group and a propylene group are more preferable, and an ethylene group is particularly preferable.
　一般式（IV）のＲ4における炭素数１～６のアルキル基としては、炭素数１～３が好ましい。また、直鎖状、分枝状及び環状のうちいずれであってもよく、直鎖状が好ましい。具体的には例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、シクロブチル基、n-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、2-メチルブチル基、1,2-ジメチルプロピル基、シクロペンチル基、n-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、2-メチルペンチル基、1,2-ジメチルブチル基、2,3-ジメチルブチル基、シクロヘキシル基等が挙げられ、中でもメチル基、エチル基、n-プロピル基、イソプロピル基が好ましく、メチル基がより好ましい。 The alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV) preferably has 1 to 3 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec -Pentyl, tert-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, 2 -Methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, cyclohexyl group and the like are mentioned, among which methyl group, ethyl group, n-propyl group and isopropyl group are preferable, and methyl group is more preferable .
　一般式（IV）のＲ3としては、無置換の炭素数２～６のアルキレン基が好ましく、無置換の炭素数２～４のアルキレン基がより好ましく、中でもエチレン基、トリメチレン基、プロピレン基、テトラメチレン基が好ましく、エチレン基、プロピレン基がより好ましく、エチレン基が特に好ましい。 R 3 in the general formula (IV) is preferably an unsubstituted alkylene group having 2 to 6 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 4 carbon atoms, among which an ethylene group, a trimethylene group, a propylene group, A tetramethylene group is preferable, an ethylene group and a propylene group are more preferable, and an ethylene group is particularly preferable.
　一般式（IV）のＲ4としては、水素原子、炭素数１～６のアルキル基が好ましく、水素原子、炭素数１～３のアルキル基がより好ましく、水素原子、メチル基が特に好ましい。 R 4 in the general formula (IV) is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.
　一般式（IV）のｖとしては、２～１０の整数が好ましく、４～１０の整数がより好ましい。また、ｖ個の－(Ｒ3－Ｏ)－基は、それぞれ同一であっても異なっていてもよい。 In general formula (IV), v is preferably an integer of 2 to 10, and more preferably an integer of 4 to 10. The v — (R 3 —O) — groups may be the same or different.
　一般式（IV）で示される基の具体例としては、ポリエチレングリコール基、メチルポリエチレングリコール基、エチルポリエチレングリコール基、n-プロピルポリエチレングリコール基、イソプロピルポリエチレングリコール基、フェニルポリエチレングリコール基、ポリトリメチレングリコール基、ポリプロピレングリコール基、メチルポリプロピレングリコール基、エチルポリプロピレングリコール基、n-プロピルポリプロピレングリコール基、イソプロピルポリプロピレングリコール基、フェニルポリプロピレングリコール基、ポリテトラメチレングリコール基、ポリペンタメチレングリコール基、ポリヘキサメチレングリコール基等が挙げられ、ポリエチレングリコール基、メチルポリエチレングリコール基、ポリプロピレングリコール基、メチルポリプロピレングリコール基が好ましく、ポリエチレングリコール基、メチルポリエチレングリコール基がより好ましい。 Specific examples of the group represented by the general formula (IV) include polyethylene glycol group, methyl polyethylene glycol group, ethyl polyethylene glycol group, n-propyl polyethylene glycol group, isopropyl polyethylene glycol group, phenyl polyethylene glycol group, polytrimethylene glycol. Group, polypropylene glycol group, methyl polypropylene glycol group, ethyl polypropylene glycol group, n-propyl polypropylene glycol group, isopropyl polypropylene glycol group, phenyl polypropylene glycol group, polytetramethylene glycol group, polypentamethylene glycol group, polyhexamethylene glycol group Polyethylene glycol group, methyl polyethylene glycol group, polypropylene glycol group Group, a methyl polypropylene glycol group preferably polyethylene glycol group, a methyl polyethylene glycol group is more preferable.
　一般式（V）のＲ5～Ｒ7における炭素数１～３のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基等が挙げられ、メチル基が好ましい。 Examples of the alkyl group having 1 to 3 carbon atoms in R 5 to R 7 in the general formula (V) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable.
　一般式（V）のＲ8における炭素数１～３のアルキレン基としては、メチレン基、エチレン基、トリメチレン基等が挙げられる。 Examples of the alkylene group having 1 to 3 carbon atoms in R 8 of the general formula (V) include a methylene group, an ethylene group, and a trimethylene group.
　一般式（V）で示される基の具体例としては、トリメチルアンモニウムメチル基、トリメチルアンモニウムエチル基、トリメチルアンモニウムプロピル基、トリエチルアンモニウムメチル基、トリエチルアンモニウムエチル基、トリエチルアンモニウムプロピル基等が挙げられる。 Specific examples of the group represented by the general formula (V) include trimethyl ammonium methyl group, trimethyl ammonium ethyl group, trimethyl ammonium propyl group, triethyl ammonium methyl group, triethyl ammonium ethyl group, triethyl ammonium propyl group and the like.
　一般式（I）のＲ1としては、水素原子又はメチル基のいずれでもよいが、Ｒ2が水素原子の場合、メチル基を表す。 R 1 in the general formula (I) may be a hydrogen atom or a methyl group, but when R 2 is a hydrogen atom, it represents a methyl group.
　一般式（I）のＲ2としては、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数７～１３のアリールアルキル基；炭素数７～１３のアリールオキシアルキル基；炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基；或いは一般式（IV）で示される基が好ましく、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数７～１３のアリールオキシアルキル基；或いは一般式（IV）で示される基がより好ましく、水素原子；或いはフッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基がさらに好ましく、ヒドロキシ基で置換された炭素数１～２０のアルキル基が特に好ましい。 R 2 in the general formula (I) is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an arylalkyl group having 7 to 13 carbon atoms. An aryloxyalkyl group having 7 to 13 carbon atoms; a hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms; or a group represented by the general formula (IV), preferably a hydrogen atom; an alkyl having 1 to 20 carbon atoms; Group: an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an aryloxyalkyl group having 7 to 13 carbon atoms; or a group represented by the general formula (IV) is more preferable; a hydrogen atom; More preferred is an alkyl group having 1 to 20 carbon atoms substituted with an atom or a hydroxy group, and particularly preferred is an alkyl group having 1 to 20 carbon atoms substituted with a hydroxy group.
　一般式（I）で示される化合物の好ましい具体例としては、下記一般式（I-I）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000097
［式中、Ｒ101は、水素原子又はメチル基を表し（但し、Ｒ102が水素原子の場合、Ｒ101はメチル基を表す）、Ｒ102は、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数７～１３のアリールアルキル基；炭素数７～１３のアリールオキシアルキル基；炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基；或いは下記一般式（IV-I）で示される基
Figure JPOXMLDOC01-appb-I000098
（式中、Ｒ103は、無置換の炭素数２～６のアルキレン基を表し、Ｒ104は、水素原子又は炭素数１～６のアルキル基を表し、ｖは上記と同じ。）を表す。］ Preferable specific examples of the compound represented by the general formula (I) include compounds represented by the following general formula (II).
Figure JPOXMLDOC01-appb-I000097
[Wherein R 101 represents a hydrogen atom or a methyl group (provided that when R 102 is a hydrogen atom, R 101 represents a methyl group), R 102 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms] An alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an arylalkyl group having 7 to 13 carbon atoms; an aryloxyalkyl group having 7 to 13 carbon atoms; hexahydrophthalimide having 9 to 14 carbon atoms; An N-alkyl group; or a group represented by the following general formula (IV-I)
Figure JPOXMLDOC01-appb-I000098
(Wherein R 103 represents an unsubstituted alkylene group having 2 to 6 carbon atoms, R 104 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and v is the same as above). ]
　一般式（I-I）のＲ102における炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数７～１３のアリールアルキル基；炭素数７～１３のアリールオキシアルキル基；及び炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基としては、一般式（I）のＲ2におけるそれらと同じものが挙げられ、好ましいものも同じである。 An alkyl group having 1 to 20 carbon atoms in R 102 of the general formula (II); an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an arylalkyl group having 7 to 13 carbon atoms; The aryloxyalkyl group having 13; and the hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms are the same as those in R 2 of the general formula (I), and preferred ones are also the same.
　一般式（IV-I）のＲ103における無置換の炭素数２～６のアルキレン基としては、炭素数２～４のものが好ましい。具体的には例えば、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が挙げられ、中でもエチレン基、トリメチレン基、プロピレン基、テトラメチレン基が好ましく、エチレン基、プロピレン基がより好ましく、エチレン基が特に好ましい。 The unsubstituted alkylene group having 2 to 6 carbon atoms in R 103 of the general formula (IV-I) is preferably one having 2 to 4 carbon atoms. Specifically, for example, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like can be mentioned, among which ethylene group, trimethylene group, propylene group and tetramethylene group are preferable, ethylene group, A propylene group is more preferable, and an ethylene group is particularly preferable.
　一般式（IV-I）のＲ104における炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkyl group having 1 to 6 carbon atoms in R 104 of the general formula (IV-I) include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). It is.
　一般式（IV-I）のＲ104としては、水素原子、炭素数１～３のアルキル基が好ましく、水素原子、メチル基がより好ましい。 R 104 in formula (IV-I) is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
　一般式（IV-I）で示される基の具体例としては、ポリエチレングリコール基、メチルポリエチレングリコール基、エチルポリエチレングリコール基、n-プロピルポリエチレングリコール基、イソプロピルポリエチレングリコール基、ポリトリメチレングリコール基、ポリプロピレングリコール基、メチルポリプロピレングリコール基、エチルポリプロピレングリコール基、n-プロピルポリプロピレングリコール基、イソプロピルポリプロピレングリコール基、ポリテトラメチレングリコール基、ポリペンタメチレングリコール基、ポリヘキサメチレングリコール基等が挙げられ、ポリエチレングリコール基、メチルポリエチレングリコール基、ポリプロピレングリコール基、メチルポリプロピレングリコール基が好ましく、ポリエチレングリコール基、メチルポリエチレングリコール基がより好ましい。 Specific examples of the group represented by the general formula (IV-I) include polyethylene glycol group, methyl polyethylene glycol group, ethyl polyethylene glycol group, n-propyl polyethylene glycol group, isopropyl polyethylene glycol group, polytrimethylene glycol group, polypropylene. Examples include glycol group, methyl polypropylene glycol group, ethyl polypropylene glycol group, n-propyl polypropylene glycol group, isopropyl polypropylene glycol group, polytetramethylene glycol group, polypentamethylene glycol group, polyhexamethylene glycol group, polyethylene glycol group Methyl polyethylene glycol group, polypropylene glycol group and methyl polypropylene glycol group are preferred. Lumpur group, more preferably a methyl polyethylene glycol group.
　一般式（I-I）のＲ101としては、水素原子又はメチル基のいずれでもよいが、Ｒ102が水素原子の場合、メチル基を表す。 R 101 in the general formula (II) may be either a hydrogen atom or a methyl group, but when R 102 is a hydrogen atom, it represents a methyl group.
　一般式（I-I）のＲ102としては、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数７～１３のアリールオキシアルキル基；或いは一般式（IV-I）で示される基が好ましく、水素原子；或いはフッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基がより好ましく、ヒドロキシ基で置換された炭素数１～２０のアルキル基が特に好ましい。 R 102 in the general formula (II) is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; aryloxyalkyl having 7 to 13 carbon atoms Or a group represented by formula (IV-I) is preferred, a hydrogen atom; or an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group is more preferred, and the number of carbon atoms substituted with a hydroxy group Particularly preferred are 1 to 20 alkyl groups.
　一般式（I）で示される化合物のより好ましい具体例としては、下記一般式（I-II）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000099
［式中、Ｒ201は、水素原子又はメチル基を表し（但し、Ｒ202が水素原子の場合、Ｒ201はメチル基を表す）、Ｒ202は、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数７～１３のアリールオキシアルキル基；或いは一般式（IV-II）で示される基
Figure JPOXMLDOC01-appb-I000100
（式中、Ｒ203は、無置換の炭素数２～４のアルキレン基を表し、Ｒ204は、水素原子又は炭素数１～３のアルキル基を表し、ｖは上記と同じ。）を表す。］ More preferred specific examples of the compound represented by the general formula (I) include compounds represented by the following general formula (I-II).
Figure JPOXMLDOC01-appb-I000099
[Wherein, R 201 represents a hydrogen atom or a methyl group (provided that when R 202 is a hydrogen atom, R 201 represents a methyl group), R 202 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms] An alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an aryloxyalkyl group having 7 to 13 carbon atoms; or a group represented by the general formula (IV-II)
Figure JPOXMLDOC01-appb-I000100
(Wherein R 203 represents an unsubstituted alkylene group having 2 to 4 carbon atoms, R 204 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and v is as defined above). ]
　一般式（I-II）のＲ202における、炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；及び炭素数７～１３のアリールオキシアルキル基としては、一般式（I）のＲ2におけるそれらと同じものが挙げられ、好ましいものも同じである。 An alkyl group having 1 to 20 carbon atoms in R 202 of formula (I-II); an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; and an aryloxyalkyl group having 7 to 13 carbon atoms Are the same as those in R 2 of the general formula (I), and preferable ones are also the same.
　一般式（IV-II）のＲ203における無置換の炭素数２～４のアルキレン基としては、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基等が挙げられ、中でもエチレン基、プロピレン基が好ましく、エチレン基がより好ましい。 Examples of the unsubstituted alkylene group having 2 to 4 carbon atoms in R 203 of the general formula (IV-II) include an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group. Among them, an ethylene group and a propylene group are preferable. An ethylene group is more preferable.
　一般式（IV-II）のＲ204における炭素数１～３のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基等が挙げられ、メチル基が好ましい。 Examples of the alkyl group having 1 to 3 carbon atoms in R204 of the general formula (IV-II) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable.
　一般式（IV-II）のＲ204としては、水素原子、メチル基が好ましい。 R 204 in formula (IV-II) is preferably a hydrogen atom or a methyl group.
　一般式（IV-II）で示される基の具体例としては、ポリエチレングリコール基、メチルポリエチレングリコール基、エチルポリエチレングリコール基、n-プロピルポリエチレングリコール基、イソプロピルポリエチレングリコール基、ポリトリメチレングリコール基、ポリプロピレングリコール基、メチルポリプロピレングリコール基、エチルポリプロピレングリコール基、n-プロピルポリプロピレングリコール基、イソプロピルポリプロピレングリコール基、ポリテトラメチレングリコール基が挙げられ、ポリエチレングリコール基、メチルポリエチレングリコール基、ポリプロピレングリコール基、メチルポリプロピレングリコール基が好ましく、ポリエチレングリコール基、メチルポリエチレングリコール基がより好ましい。 Specific examples of the group represented by the general formula (IV-II) include polyethylene glycol group, methyl polyethylene glycol group, ethyl polyethylene glycol group, n-propyl polyethylene glycol group, isopropyl polyethylene glycol group, polytrimethylene glycol group, polypropylene. Examples include glycol group, methyl polypropylene glycol group, ethyl polypropylene glycol group, n-propyl polypropylene glycol group, isopropyl polypropylene glycol group, polytetramethylene glycol group, polyethylene glycol group, methyl polyethylene glycol group, polypropylene glycol group, methyl polypropylene glycol. Group is preferable, and polyethylene glycol group and methyl polyethylene glycol group are more preferable.
　一般式（I-II）のＲ201としては、水素原子又はメチル基のいずれでもよいが、Ｒ202が水素原子の場合、メチル基を表す。 R 201 in the general formula (I-II) may be either a hydrogen atom or a methyl group, but when R 202 is a hydrogen atom, it represents a methyl group.
　一般式（I-II）のＲ202としては、水素原子、或いはフッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基がより好ましく、ヒドロキシ基で置換された炭素数１～２０のアルキル基が特に好ましい。 R 202 in the general formula (I-II) is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group, and preferably having 1 to 20 carbon atoms substituted with a hydroxy group. Alkyl groups are particularly preferred.
　一般式（I）で示される化合物の特に好ましい具体例としては、例えばメタクリル酸、（メタ）アクリル酸-n-ブチル、（メタ）アクリル酸-n-ペンチル、（メタ）アクリル酸-n-ヘキシル、（メタ）アクリル酸トリフルオロメチル、（メタ）アクリル酸トリフルオロエチル、（メタ）アクリル酸(パーフルオロブチル)メチル、（メタ）アクリル酸-2-(パーフルオロブチル)エチル、（メタ）アクリル酸(パーフルオロヘキシル)メチル、（メタ）アクリル酸-2-(パーフルオロヘキシル)エチル、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸フェノキシメチル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸フェノキシプロピル、ポリエチレングリコール（メタ）アクリレート、ポリエチレングリコールモノメチルエーテル（メタ）アクリレート等が挙げられ、中でも、メタクリル酸、（メタ）アクリル酸-2-(パーフルオロブチル)エチル、（メタ）アクリル酸-2-(パーフルオロヘキシル)エチル、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシルが好ましく、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチルがより好ましく、（メタ）アクリル酸ヒドロキシエチルが特に好ましい。一般式（I）で示される化合物は、市販のものでも、自体公知の方法によって適宜合成したものでもよい。 Particularly preferred specific examples of the compound represented by the general formula (I) include, for example, methacrylic acid, (meth) acrylic acid-n-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl. , (Meth) acrylic acid trifluoromethyl, (meth) acrylic acid trifluoroethyl, (meth) acrylic acid (perfluorobutyl) methyl, (meth) acrylic acid-2- (perfluorobutyl) ethyl, (meth) acrylic Acid (perfluorohexyl) methyl, (meth) acrylic acid-2- (perfluorohexyl) ethyl, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) Hydroxybutyl acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, (meth) acrylic Examples include phenoxymethyl oxalate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, among others, methacrylic acid, (meth) acrylic Acid-2- (perfluorobutyl) ethyl, (meth) acrylic acid-2- (perfluorohexyl) ethyl, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl (meth) acrylate are preferred, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy (meth) acrylate Propyl, (meth) more preferably butyl hydroxy acrylate, hydroxyethyl (meth) acrylate is particularly preferred. The compound represented by the general formula (I) may be a commercially available product or a compound appropriately synthesized by a method known per se.
　一般式（II）のＲ12及びＲ13における炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられ、中でもメチル基、エチル基、n-プロピル基、イソプロピル基が好ましく、イソプロピル基がより好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms in R 12 and R 13 of the general formula (II) include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). , An ethyl group, an n-propyl group and an isopropyl group are preferable, and an isopropyl group is more preferable.
　一般式（II）のＲ13における炭素数３～９のジアルキルアミノアルキル基としては、ジメチルアミノメチル基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジエチルアミノメチル基、ジエチルアミノエチル基、ジエチルアミノプロピル基、ジプロピルアミノメチル基、ジプロピルアミノエチル基、ジプロピルアミノプロピル基等が挙げられる。 Examples of the dialkylaminoalkyl group having 3 to 9 carbon atoms in R 13 of the general formula (II) include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, A propylaminomethyl group, a dipropylaminoethyl group, a dipropylaminopropyl group, etc. are mentioned.
　一般式（II）のＲ13における炭素数１～６のヒドロキシアルキル基としては、末端部分がヒドロキシ基で置換されたものが好ましい。また、１～２個の水素がヒドロキシ基で置換されたものが好ましく、１個の水素がヒドロキシ基で置換されたものがより好ましい。さらに、炭素数１～３のものが好ましく、直鎖状が好ましい。具体的には例えば、ヒドロキシメチル基、ヒドロキシエチル基、ジヒドロキシエチル基、ヒドロキシプロピル基、ジヒドロキシプロピル基、ヒドロキシブチル基、ジヒドロキシブチル基、ヒドロキシペンチル基、ジヒドロキシペンチル基、ヒドロキシヘキシル基、ジヒドロキシヘキシル基が挙げられ、中でもヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシヘキシル基が好ましく、ヒドロキシエチル基がより好ましい。 As the hydroxyalkyl group having 1 to 6 carbon atoms in R 13 of the general formula (II), those having a terminal portion substituted with a hydroxy group are preferred. In addition, one in which one or two hydrogens are substituted with a hydroxy group is preferable, and one in which one hydrogen is substituted with a hydroxy group is more preferable. Further, those having 1 to 3 carbon atoms are preferred, and a straight chain is preferred. Specifically, for example, hydroxymethyl group, hydroxyethyl group, dihydroxyethyl group, hydroxypropyl group, dihydroxypropyl group, hydroxybutyl group, dihydroxybutyl group, hydroxypentyl group, dihydroxypentyl group, hydroxyhexyl group, dihydroxyhexyl group Among them, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group are preferable, and a hydroxyethyl group is more preferable.
　一般式（II）のＲ11としては、水素原子が好ましい。 R 11 in the general formula (II) is preferably a hydrogen atom.
　一般式（II）のＲ12としては、水素原子、炭素数１～３のアルキル基が好ましく、水素原子がより好ましい。 R 12 in the general formula (II) is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　一般式（II）のＲ13としては、水素原子、炭素数１～６のアルキル基、炭素数１～６のヒドロキシアルキル基が好ましく、水素原子、炭素数１～６のアルキル基がより好ましく、水素原子、炭素数１～３のアルキル基がさらに好ましく、水素原子が特に好ましい。 R 13 in the general formula (II) is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A hydrogen atom and an alkyl group having 1 to 3 carbon atoms are more preferable, and a hydrogen atom is particularly preferable.
　一般式（II）で示される化合物の好ましい具体例としては、下記一般式（II-I）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000101
（式中、Ｒ113は、水素原子、炭素数１～６のアルキル基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ11及びＲ12は上記と同じ。） Preferable specific examples of the compound represented by the general formula (II) include compounds represented by the following general formula (II-I).
Figure JPOXMLDOC01-appb-I000101
(Wherein R 113 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, and R 11 and R 12 are the same as above).
　一般式（II-I）のＲ113における炭素数１～６のアルキル基及び炭素数１～６のヒドロキシアルキル基としては、一般式（II）のＲ13におけるそれらと同じものが挙げられ、好ましいものも同じである。 Examples of the alkyl group having 1 to 6 carbon atoms and the hydroxyalkyl group having 1 to 6 carbon atoms in R 113 of the general formula (II-I) include the same as those in R 13 of the general formula (II), and are preferable. The same is true.
　一般式（II-I）のＲ113としては、水素原子、炭素数１～６のアルキル基が好ましく、水素原子、炭素数１～３のアルキル基がより好ましく、水素原子が特に好ましい。 R 113 in formula (II-I) is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom.
　一般式（II）で示される化合物のより好ましい具体例としては、下記一般式（II-II）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000102
（式中、Ｒ212及びＲ213は、それぞれ独立して水素原子又は炭素数１～３のアルキル基を表し、Ｒ11は上記と同じ。） More preferred specific examples of the compound represented by the general formula (II) include compounds represented by the following general formula (II-II).
Figure JPOXMLDOC01-appb-I000102
(Wherein R 212 and R 213 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 11 is the same as above).
　一般式（II-II）のＲ212及びＲ213における炭素数１～３のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基等が挙げられ、イソプロピル基が好ましい。 Examples of the alkyl group having 1 to 3 carbon atoms in R 212 and R 213 in the general formula (II-II) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and an isopropyl group is preferable.
　一般式（II-II）のＲ212及びＲ213としては、水素原子が好ましい。 As R 212 and R 213 in formula (II-II), a hydrogen atom is preferable.
　一般式（II）で示される化合物の特に好ましい具体例としては、例えば（メタ）アクリルアミド、N-メチル（メタ）アクリルアミド、N-エチル（メタ）アクリルアミド、N-n-プロピル（メタ）アクリルアミド、N-イソプロピル（メタ）アクリルアミド、N,N-ジメチル（メタ）アクリルアミド、N,N-ジエチル（メタ）アクリルアミド、N,N-ジ-n-プロピル（メタ）アクリルアミド、N,N-ジイソプロピル（メタ）アクリルアミド等が挙げられ、（メタ）アクリルアミド、N-メチル（メタ）アクリルアミド、N-エチル（メタ）アクリルアミド、N-n-プロピル（メタ）アクリルアミド、N-イソプロピル（メタ）アクリルアミド、N,N-ジメチル（メタ）アクリルアミドが好ましく、（メタ）アクリルアミドがより好ましく、アクリルアミドが特に好ましい。一般式（II）で示される化合物は、市販のものでも、自体公知の方法によって適宜合成したものでもよい。 Particularly preferred specific examples of the compound represented by the general formula (II) include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide etc. (Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide (Meth) acrylamide is more preferable, and acrylamide is particularly preferable. The compound represented by the general formula (II) may be commercially available or may be appropriately synthesized by a method known per se.
　本発明に係るコポリマーの構成成分の組合せとしては、下記表記載の組合せが挙げられ、中でも組合せ１～４が好ましく、組合せ１、３及び４がより好ましく、組合せ１が特に好ましい。さらに、組合せ１の中でも、アクリル酸由来のモノマー単位と一般式（I-I）で示される化合物由来のモノマー単位１種とからなる組合せが好ましく、アクリル酸由来のモノマー単位と一般式（I-II）で示される化合物由来のモノマー単位１種とからなる組合せがより好ましい。より具体的には、アクリル酸由来のモノマー単位と、一般式（I）で示される化合物の特に好ましい具体例として挙げられている化合物由来のモノマー単位１種とからなる組合せが好ましい。 The combinations of the constituent components of the copolymer according to the present invention include combinations described in the following table, among which combinations 1 to 4 are preferable, combinations 1, 3 and 4 are more preferable, and combination 1 is particularly preferable. Furthermore, among the combinations 1, a combination comprising a monomer unit derived from acrylic acid and one monomer unit derived from the compound represented by the general formula (II) is preferable, and the monomer unit derived from acrylic acid and the general formula (I-II) The combination which consists of 1 type of monomer units derived from the compound shown by these is more preferable. More specifically, a combination comprising a monomer unit derived from acrylic acid and one kind of monomer unit derived from the compound listed as a particularly preferred specific example of the compound represented by formula (I) is preferable.
Figure JPOXMLDOC01-appb-I000103
Figure JPOXMLDOC01-appb-I000103
　本発明に係るコポリマーにおける、アクリル酸由来のモノマー単位と、一般式（I）又は一般式（II）で示される化合物由来のモノマー単位の比率は、質量比として通常、アクリル酸由来のモノマー単位／一般式（I）又は一般式（II）で示される化合物由来のモノマー単位＝３０／７０～７０／３０であり、好ましくは４０／６０～６０／４０である。 In the copolymer according to the present invention, the ratio of the monomer unit derived from acrylic acid and the monomer unit derived from the compound represented by the general formula (I) or (II) is usually a mass ratio of monomer units derived from acrylic acid / Monomer units derived from the compound represented by formula (I) or formula (II) = 30/70 to 70/30, preferably 40/60 to 60/40.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーにおけるポリアクリル酸の含有量は、（Ａ）の総質量に対して５０～１００質量％、好ましくは７０～１００質量％、より好ましくは７５～１００質量％である。尚、ここでいう「１００質量％」とは、（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ１）ポリアクリル酸のみである場合を示す。 The content of polyacrylic acid in one or more polymers containing (A) polyacrylic acid is 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 75 to 100% by mass with respect to the total mass of (A). 100% by mass. In addition, "100 mass%" here shows the case where the 1 or more types of polymer containing (A) polyacrylic acid is only (A1) polyacrylic acid.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーは中和されたものであってもよい。言い換えれば、（Ａ）ポリアクリル酸を含む１種以上のポリマーのうちカルボキシ基を有するモノマー単位を構成成分に含むポリマーにおいて、該ポリマー中のカルボキシ基の一部又は全部が塩になっていてもよい。（Ａ）ポリアクリル酸を含む１種以上のポリマーとしては、該ポリマーのうちいずれか１種以上が中和されたものが好ましく、該ポリマーのうち少なくともポリアクリル酸が中和されたものがより好ましく、全てのポリマーが中和されたものがさらに好ましい。（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ１）ポリアクリル酸のみである場合、中和されたポリアクリル酸が好ましく；（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ２）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群である場合、該ポリマー群中の少なくとも１種のポリマーが中和されたものが好ましく、少なくともポリアクリル酸が中和されたものがより好ましく、該ポリマー群中の全てのポリマーが中和されたものがさらに好ましい。中和されたポリマーとしては、水酸化ナトリウム、水酸化リチウム、水酸化カリウム等のアルカリ金属で中和されたものが好ましく、水酸化ナトリウムで中和されたものがより好ましい。このような中和されたポリマーを用いると電極部材の分散性が向上し、活物質と導電性化合物とを集電体上に均一に分布させることができるため、電極の電気特性をより向上させることが可能となる。この際の中和度は、通常６０～１００％、好ましくは７０～１００％、より好ましくは７０～９０％である。 (A) One or more polymers including polyacrylic acid may be neutralized. In other words, in (A) a polymer containing a monomer unit having a carboxy group as a constituent component among one or more polymers containing polyacrylic acid, a part or all of the carboxy group in the polymer may be a salt. Good. (A) As one or more types of polymers containing polyacrylic acid, those in which any one or more of the polymers are neutralized are preferable, and those in which at least polyacrylic acid is neutralized are more preferable. Preferably, all polymers are neutralized. When (A) the one or more polymers containing polyacrylic acid are (A1) only polyacrylic acid, neutralized polyacrylic acid is preferred; (A) one or more polymers containing polyacrylic acid are ( A2) In the case of a polymer group composed of polyacrylic acid and one or more polymers other than polyacrylic acid, it is preferable that at least one polymer in the polymer group is neutralized, and at least polyacrylic acid is neutralized. More preferred are those obtained by neutralizing all polymers in the polymer group. The neutralized polymer is preferably neutralized with an alkali metal such as sodium hydroxide, lithium hydroxide, or potassium hydroxide, and more preferably neutralized with sodium hydroxide. When such a neutralized polymer is used, the dispersibility of the electrode member is improved, and the active material and the conductive compound can be uniformly distributed on the current collector, thereby further improving the electrical characteristics of the electrode. It becomes possible. The degree of neutralization at this time is usually 60 to 100%, preferably 70 to 100%, more preferably 70 to 90%.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーは架橋されたものであってもよい。（Ａ）ポリアクリル酸を含む１種以上のポリマーとしては、該ポリマーのうちいずれか１種以上が架橋されたものが好ましく、該ポリマーのうち少なくともポリアクリル酸が架橋されたものがより好ましく、全てのポリマーが架橋されたものがさらに好ましい。（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ１）ポリアクリル酸のみである場合、架橋されたポリアクリル酸が好ましく；（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ２）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群である場合、該ポリマー群中の少なくとも１種のポリマーが架橋されたものが好ましく、少なくともポリアクリル酸が架橋されたものがより好ましく、該ポリマー群中の全てのポリマーが架橋されたものがさらに好ましい。尚、該ポリマーの架橋に用いられる架橋剤としては、後述する一般式［１］～［１３］記載の化合物及び一般式［１４］記載のポリマーから選ばれる架橋剤が挙げられる（以下、本発明に係る架橋剤と略記する場合がある）。また、上記架橋されたポリマーは、さらに中和されたものであってもよい。 (A) One or more polymers containing polyacrylic acid may be cross-linked. (A) As one or more kinds of polymers containing polyacrylic acid, those in which any one or more of the polymers are cross-linked are preferable, and those in which at least polyacrylic acid is cross-linked are more preferable. More preferably, all polymers are crosslinked. When (A) one or more polymers containing polyacrylic acid is (A1) polyacrylic acid alone, crosslinked polyacrylic acid is preferred; (A) one or more polymers containing polyacrylic acid are (A2 ) In the case of a polymer group consisting of polyacrylic acid and one or more polymers other than polyacrylic acid, it is preferable that at least one polymer in the polymer group is cross-linked, and at least polyacrylic acid is cross-linked Are more preferable, and those in which all the polymers in the polymer group are crosslinked are more preferable. Examples of the crosslinking agent used for crosslinking the polymer include a crosslinking agent selected from compounds described in the following general formulas [1] to [13] and a polymer described in the general formula [14] (hereinafter referred to as the present invention). May be abbreviated as a crosslinking agent). Further, the crosslinked polymer may be further neutralized.
　架橋されたポリマーの粘度としては、回転粘度計の回転速度が12rpmの場合、通常500～50,000mPa・S、好ましくは1,000～50,000mPa・Sである。尚、回転粘度計は、回転速度12rpmにおいて上限粘度が50,000mPa・Sであるものを用いた。該粘度は、各ポリマーを１質量％の濃度で水に分散（懸濁）させたものを、２０～２５℃でＢ型回転粘度計にて測定した値である。 The viscosity of the crosslinked polymer is usually 500 to 50,000 mPa · S, preferably 1,000 to 50,000 mPa · S when the rotational speed of the rotational viscometer is 12 rpm. A rotational viscometer having an upper limit viscosity of 50,000 mPa · S at a rotational speed of 12 rpm was used. The viscosity is a value obtained by dispersing (suspending) each polymer in water at a concentration of 1% by mass at 20 to 25 ° C. using a B-type rotational viscometer.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーとしては、該ポリマーのうちいずれか１種以上が本発明に係る架橋剤により架橋されたものが好ましく；該ポリマーのうち少なくともポリアクリル酸が本発明に係る架橋剤により架橋されたものがより好ましく；該ポリマー全てが本発明に係る架橋剤により架橋されたものがさらに好ましく；該ポリマー全てが本発明に係る架橋剤により架橋され、且つ中和されたものが特に好ましい。
　（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ１）ポリアクリル酸のみである場合、本発明に係る架橋剤により架橋されたポリアクリル酸が好ましく；本発明に係る架橋剤により架橋され、且つ中和されたポリアクリル酸がより好ましい。（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ２）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群である場合、該ポリマー群中の少なくとも１種のポリマーが本発明に係る架橋剤により架橋されたものが好ましく；少なくともポリアクリル酸が本発明に係る架橋剤により架橋されたものがより好ましく；該ポリマー群中の全てのポリマーが本発明に係る架橋剤により架橋されたものがさらに好ましく；該ポリマー群中の全てのポリマーが本発明に係る架橋剤により架橋され、且つ中和されたものがさらに好ましい。 (A) As one or more types of polymers containing polyacrylic acid, those in which at least one of the polymers is cross-linked by the cross-linking agent according to the present invention are preferred; More preferred are those crosslinked with the crosslinking agent according to the invention; more preferred are all the polymers crosslinked with the crosslinking agent according to the invention; and all the polymers are crosslinked with the crosslinking agent according to the invention and are neutralized. Particularly preferred are
When (A) at least one polymer containing polyacrylic acid is only (A1) polyacrylic acid, polyacrylic acid crosslinked with the crosslinking agent according to the present invention is preferred; crosslinked with the crosslinking agent according to the present invention. And neutralized polyacrylic acid is more preferred. When (A) at least one polymer containing polyacrylic acid is a polymer group comprising (A2) a polymer other than polyacrylic acid and at least one polyacrylic acid, at least one polymer in the polymer group is Those crosslinked by the crosslinking agent according to the present invention are preferred; at least polyacrylic acid is more preferably crosslinked by the crosslinking agent according to the present invention; all polymers in the polymer group are formed by the crosslinking agent according to the present invention. More preferred are those that have been cross-linked; more preferred are those in which all polymers in the group of polymers have been cross-linked and neutralized by the cross-linking agent according to the present invention.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーそれぞれの重量平均分子量は、通常1,000～10,000,000、好ましくは10,000～5,000,000である。 (A) The weight average molecular weight of each of the one or more polymers including polyacrylic acid is usually 1,000 to 10,000,000, preferably 10,000 to 5,000,000.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーにおける（Ａ１）ポリアクリル酸のみとしては、（Ａ１－１）本発明に係る架橋剤により架橋されたポリアクリル酸が好ましく、（Ａ１－２）本発明に係る架橋剤により架橋され、且つ中和されたポリアクリル酸がより好ましい。 (A1) The polyacrylic acid alone in (A1) one or more polymers containing polyacrylic acid is preferably (A1-1) polyacrylic acid crosslinked with a crosslinking agent according to the present invention, (A1-2) Polyacrylic acid crosslinked and neutralized by the crosslinking agent according to the present invention is more preferred.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーにおける（Ａ２）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群としては、（Ａ２－１）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群であり、ポリアクリル酸以外のポリマーがカルボキシ基を有するモノマー単位を構成成分に含むポリマーであるものが好ましく、（Ａ２－２）ポリアクリル酸と１種以上のコポリマーからなるポリマー群であり、該コポリマーがカルボキシ基を有するモノマー単位を構成成分に含むコポリマーであるものがより好ましく、（Ａ２－３）ポリアクリル酸と１種以上のコポリマーからなるポリマー群であり、該コポリマーがアクリル酸由来のモノマー単位を構成成分に含むコポリマーであるものがさらに好ましく、（Ａ２－４）ポリアクリル酸と１種以上のコポリマーからなるポリマー群であり、該コポリマーがアクリル酸由来のモノマー単位を構成成分に含むコポリマーであり、さらに該ポリマー群中に少なくとも本発明に係るコポリマーを含むものが特に好ましく、（Ａ２－５）ポリアクリル酸及び本発明に係るコポリマーが最も好ましい。 (A) One or more polymers containing polyacrylic acid (A2) The polymer group consisting of polymers other than polyacrylic acid and one or more polyacrylic acids includes (A2-1) polyacrylic acid and one or more polymers. A polymer group consisting of a polymer other than polyacrylic acid, wherein the polymer other than polyacrylic acid is preferably a polymer containing a monomer unit having a carboxy group as a constituent component. (A2-2) Polyacrylic acid and one kind More preferably, it is a polymer group comprising the above copolymers, and the copolymer is a copolymer comprising a monomer unit having a carboxy group as a constituent component. (A2-3) Polymer group comprising polyacrylic acid and one or more copolymers And the copolymer is a copolymer containing a monomer unit derived from acrylic acid as a constituent component. Is more preferably (A2-4) a polymer group consisting of polyacrylic acid and one or more copolymers, and the copolymer is a copolymer containing a monomer unit derived from acrylic acid as a constituent, and at least in the polymer group Particularly preferred are those comprising the copolymers according to the invention, with (A2-5) polyacrylic acid and the copolymers according to the invention being most preferred.
　（Ａ２－５）ポリアクリル酸及び本発明に係るコポリマーの中でも、（Ａ２－５－１）ポリアクリル酸及び本発明に係るコポリマーであり、ポリアクリル酸及び／又は本発明に係るコポリマーが本発明に係る架橋剤により架橋されたものが好ましく；（Ａ２－５－２）ポリアクリル酸及び本発明に係るコポリマーであり、少なくともポリアクリル酸が本発明に係る架橋剤により架橋されたものがより好ましく；（Ａ２－５－３）ポリアクリル酸及び本発明に係るコポリマーであり、ポリアクリル酸及び本発明に係るコポリマーが本発明に係る架橋剤により架橋されたものがさらに好ましく；（Ａ２－５－４）ポリアクリル酸及び本発明に係るコポリマーであり、該ポリアクリル酸及び本発明に係るコポリマーが本発明に係る架橋剤により架橋され、且つ少なくともポリアクリル酸が中和されたものがさらに好ましく；（Ａ２－５－５）本発明に係る架橋剤により架橋され、且つ中和されたポリアクリル酸、及び本発明に係る架橋剤により架橋され、且つ中和された本発明に係るコポリマーが特に好ましい。 Among the (A2-5) polyacrylic acid and the copolymer according to the present invention, (A2-5-1) polyacrylic acid and the copolymer according to the present invention, and the polyacrylic acid and / or the copolymer according to the present invention are the present invention. (A2-5-2) Polyacrylic acid and the copolymer according to the present invention are preferred, and at least polyacrylic acid is preferably crosslinked with the crosslinking agent according to the present invention. (A2-5-3) polyacrylic acid and a copolymer according to the present invention, wherein polyacrylic acid and the copolymer according to the present invention are more preferably cross-linked by a cross-linking agent according to the present invention; 4) Polyacrylic acid and the copolymer according to the present invention, wherein the polyacrylic acid and the copolymer according to the present invention are bridged by the crosslinking agent according to the present invention. More preferably, the polyacrylic acid is at least neutralized with polyacrylic acid; (A2-5-5) cross-linked and neutralized with the cross-linking agent according to the present invention, and the cross-linking agent according to the present invention. Particularly preferred are copolymers according to the invention which have been crosslinked and neutralized by
　（Ａ）ポリアクリル酸を含む１種以上のポリマーとしては、上記（Ａ１）及び（Ａ２－５）が好ましく、上記（Ａ１－１）及び（Ａ２－５－１）がより好ましく、上記（Ａ１－１）及び（Ａ２－５－２）がさらに好ましく、上記（Ａ１－１）及び（Ａ２－５－３）が特に好ましく、上記（Ａ１－２）及び（Ａ２－５－５）が最も好ましい。 (A) The one or more polymers containing polyacrylic acid are preferably the above (A1) and (A2-5), more preferably the above (A1-1) and (A2-5-1), and the above (A1 -1) and (A2-5-2) are more preferable, (A1-1) and (A2-5-3) are particularly preferable, and (A1-2) and (A2-5-5) are most preferable. .
［本発明に係る架橋剤］
　（Ａ）ポリアクリル酸を含む１種以上のポリマーの架橋に用いられる架橋剤としては、下記一般式［１］～［１３］記載の化合物及び下記一般式［１４］記載のポリマーから選ばれる架橋剤が挙げられる。 [Crosslinking agent according to the present invention]
(A) The crosslinking agent used for crosslinking one or more polymers containing polyacrylic acid is a compound selected from the compounds represented by the following general formulas [1] to [13] and the polymer represented by the following general formula [14]. Agents.
Figure JPOXMLDOC01-appb-I000104
（式中、ａは１～６の整数を表す。）
Figure JPOXMLDOC01-appb-I000104
(Wherein, a represents an integer of 1 to 6)
Figure JPOXMLDOC01-appb-I000105
［式中、Ｒ25及びＲ26は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ21は、炭素数１～２０のアルキレン基、下記一般式［２－１］で示される基
Figure JPOXMLDOC01-appb-I000106
（式中、Ｒ22は、炭素数１～６のアルキレン基を表し、ｂは１～６の整数を表す。）、又は下記一般式［２－２］で示される基
Figure JPOXMLDOC01-appb-I000107
（式中、Ｒ23及びＲ24は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｃは１～２２の整数を表す。）を表す。］
Figure JPOXMLDOC01-appb-I000105
[Wherein R 25 and R 26 each independently represent a hydrogen atom or a methyl group, R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1]
Figure JPOXMLDOC01-appb-I000106
(Wherein R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6), or a group represented by the following general formula [2-2]
Figure JPOXMLDOC01-appb-I000107
(Wherein R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22). ]
Figure JPOXMLDOC01-appb-I000108
（式中、Ｒ27～Ｒ33は、それぞれ独立して、炭素数１～３のアルキレン基を表す。）
Figure JPOXMLDOC01-appb-I000108
(In the formula, R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms.)
Figure JPOXMLDOC01-appb-I000109
（式中、Ｒ34～Ｒ37は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｄは１～６の整数を表し、ｅは０～６の整数を表し、ｆ及びｇはそれぞれ独立して０又は１の整数を表す。）
Figure JPOXMLDOC01-appb-I000109
(Wherein R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms, d represents an integer of 1 to 6, e represents an integer of 0 to 6, f and g Each independently represents an integer of 0 or 1.)
Figure JPOXMLDOC01-appb-I000110
（式中、Ｒ38～Ｒ45は、それぞれ独立して、水素原子、ビニル基又はビニルケトン基を表し、これらの少なくとも２つ以上はビニル基又はビニルケトン基である。）
Figure JPOXMLDOC01-appb-I000110
(Wherein R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group.)
Figure JPOXMLDOC01-appb-I000111
（式中、Ｒ46～Ｒ48は、それぞれ独立して、炭素数１～６のアルキレン基を表す。）
Figure JPOXMLDOC01-appb-I000111
(Wherein R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms.)
Figure JPOXMLDOC01-appb-I000112
（式中、環Ar1は、ベンゼン環又はナフタレン環を表し、Ｒ49は、炭素数１～６のアルキレン基を表し、ｈは２～４の整数を表す。）
Figure JPOXMLDOC01-appb-I000112
(In the formula, ring Ar 1 represents a benzene ring or a naphthalene ring, R 49 represents an alkylene group having 1 to 6 carbon atoms, and h represents an integer of 2 to 4).
Figure JPOXMLDOC01-appb-I000113
（式中、環Ar2及び環Ar3は、それぞれ独立して、ベンゼン環又はナフタレン環を表し、Ｒ50は、炭素数１～６のアルキレン基を表す。）
Figure JPOXMLDOC01-appb-I000113
(In the formula, each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring, and R 50 represents an alkylene group having 1 to 6 carbon atoms.)
Figure JPOXMLDOC01-appb-I000114
（式中、環Ar4は、ベンゼン環又はナフタレン環を表す。）
Figure JPOXMLDOC01-appb-I000114
(In the formula, Ar 4 represents a benzene ring or a naphthalene ring.)
Figure JPOXMLDOC01-appb-I000115
（式中、ｉは０～６の整数を表す。）
Figure JPOXMLDOC01-appb-I000115
(In the formula, i represents an integer of 0 to 6.)
Figure JPOXMLDOC01-appb-I000116
（式中、Ｒ51は、炭素数１～６のアルキレン基を表す。）
Figure JPOXMLDOC01-appb-I000116
(In the formula, R 51 represents an alkylene group having 1 to 6 carbon atoms.)
Figure JPOXMLDOC01-appb-I000117
［式中、Ｒ52は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１２－１］で示される基
Figure JPOXMLDOC01-appb-I000118
（式中、Ｒ53は、炭素数１～６のアルキル基を表し、Ｒ54は、炭素数１～６のアルキレン基を表し、環Ar5は、ベンゼン環又はナフタレン環を表し、ｊは、０～４の整数を表す。）、或いは、下記一般式［１２－２］で示される基
Figure JPOXMLDOC01-appb-I000119
（式中、Ｒ55は、炭素数１～６のアルキレン基を表し、Ｒ53、Ｒ54、環Ar5及びｊは、上記と同じ。）を表す。］
Figure JPOXMLDOC01-appb-I000117
[Wherein R 52 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [12-1] Group represented by
Figure JPOXMLDOC01-appb-I000118
(Wherein R 53 represents an alkyl group having 1 to 6 carbon atoms, R 54 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 5 represents a benzene ring or a naphthalene ring, j is Represents an integer of 0 to 4, or a group represented by the following general formula [12-2]
Figure JPOXMLDOC01-appb-I000119
(Wherein R 55 represents an alkylene group having 1 to 6 carbon atoms, and R 53 , R 54 , and rings Ar 5 and j are the same as above). ]
Figure JPOXMLDOC01-appb-I000120
［式中、Ｒ56及びＲ57は、それぞれ独立して、置換基を有する又は無置換の炭素数１～６のアルキル基、置換基を有する又は無置換の炭素数６～１０のアリール基、或いは、下記一般式［１３－１］で示される基
Figure JPOXMLDOC01-appb-I000121
（式中、Ｒ58は、炭素数１～６のアルキル基を表し、Ｒ59は、炭素数１～６のアルキレン基を表し、環Ar6は、ベンゼン環又はナフタレン環を表し、ｋは、０～５の整数を表す。）を表す。］
Figure JPOXMLDOC01-appb-I000120
[Wherein, R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1]
Figure JPOXMLDOC01-appb-I000121
(Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5). ]
Figure JPOXMLDOC01-appb-I000122
［式中、Ｒ60は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１４－１］又は［１４－２］で示される基
Figure JPOXMLDOC01-appb-I000123
（式中、Ｒ61は、炭素数１～６のアルキル基を表し、Ｒ62は、炭素数１～６のアルキレン基を表し、環Ar7は、ベンゼン環又はナフタレン環を表し、ｐは、０～４の整数を表す。）、或いは、下記一般式［１４－３］で示される基
Figure JPOXMLDOC01-appb-I000124
（式中、Ｒ63は、炭素数１～６のアルキレン基を表し、Ｒ61、Ｒ62、環Ar7及びｐは、上記と同じ。）を表し、ｍは１０～１００００の整数を表す。］
Figure JPOXMLDOC01-appb-I000122
[Wherein R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2]
Figure JPOXMLDOC01-appb-I000123
(Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3]
Figure JPOXMLDOC01-appb-I000124
(Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000. ]
　一般式［１］におけるａとしては、１～３の整数が好ましく、１がより好ましい。 In the general formula [1], a is preferably an integer of 1 to 3, and more preferably 1.
　一般式［１］記載の化合物の具体例としては、例えばアクリル酸アリル（アクリル酸-2-プロペニル）、アクリル酸-3-ブテニル、アクリル酸-4-ペンテニル、アクリル酸-5-ヘキシニル、アクリル酸-6-ヘプテニル、アクリル酸-7-オクテニル等が挙げられ、アクリル酸アリルが好ましい。 Specific examples of the compound represented by the general formula [1] include, for example, allyl acrylate (acrylic acid-2-propenyl), acrylic acid-3-butenyl, acrylic acid-4-pentenyl, acrylic acid-5-hexynyl, and acrylic acid. -6-heptenyl, -7-octenyl acrylate, and the like, and allyl acrylate is preferred.
　一般式［２］のＲ21における炭素数１～２０のアルキレン基としては、炭素数１～１２のものが好ましく、炭素数１～６のものがより好ましい。また、直鎖状、分枝状及び環状のうちいずれであってもよく、直鎖状が好ましい。具体的には例えば、メチレン基、エチレン基、メチルメチレン基、トリメチレン基、プロピレン基、ジメチルメチレン基、エチルメチレン基、テトラメチレン基、1-メチルトリメチレン基、2-メチルトリメチレン基、1,2-ジメチルエチレン基、1,1-ジメチルエチレン基、エチルエチレン基、エチルメチルメチレン基、プロピルメチレン基、ペンタメチレン基、1-メチルテトラメチレン基、2-メチルテトラメチレン基、1-エチルトリメチレン基、2-エチルトリメチレン基、n-プロピルエチレン基、イソプロピルエチレン基、n-ブチルメチレン基、イソブチルメチレン基、tert-ブチルメチレン基、ヘキサメチレン基、1-メチルペンタメチレン基、2-メチルペンタメチレン基、3-メチルペンタメチレン基、1-エチルテトラメチレン基、2-エチルテトラメチレン基、1-n-プロピルトリメチレン基、1-イソプロピルトリメチレン基、2-n-プロピルトリメチレン基、2-イソプロピルトリメチレン基、n-ブチルエチレン基、イソブチルエチレン基、tert-ブチルエチレン基、n-ペンチルメチレン基、イソペンチルメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、トリデカメチレン基、テトラデカメチレン基、ペンタデカメチレン基、ヘキサデカメチレン基、ヘプタデカメチレン基、オクタデカメチレン基、ノナデカメチレン基、イコサメチレン基、シクロプロピレン基、シクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基、シクロウンデシレン基、シクロドデシレン基、シクロトリデシレン基、シクロヘキサデシレン基、シクロオクタデシレン基、シクロイコシレン基、-Ｃ6Ｈ10-ＣＨ2-基、-Ｃ6Ｈ10-Ｃ2Ｈ4-基、-Ｃ6Ｈ10-Ｃ3Ｈ6-基、-Ｃ6Ｈ10-Ｃ4Ｈ8-基、-Ｃ6Ｈ10-Ｃ5Ｈ10-基、-Ｃ6Ｈ10-Ｃ6Ｈ12-基等が挙げられ、中でも、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基が好ましく、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基がより好ましい。 The alkylene group having 1 to 20 carbon atoms in R 21 of the general formula [2] preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable. Specifically, for example, methylene group, ethylene group, methylmethylene group, trimethylene group, propylene group, dimethylmethylene group, ethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group Group, 2-ethyltrimethylene group, n-propylethylene group, isopropylethylene group, n-butylmethylene group, isobutylmethylene group, tert-butylmethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpenta Methylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group 1-n-propyltrimethylene group, 1-isopropyltrimethylene group, 2-n-propyltrimethylene group, 2-isopropyltrimethylene group, n-butylethylene group, isobutylethylene group, tert-butylethylene group, n- Pentylmethylene group, isopentylmethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group Group, heptadecamethylene group, octadecamethylene group, nonadecamethylene group, icosamethylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group , Cyclododecy Down group, cyclotrimethylene decylene group, cyclohexadecen cyclohexylene group, a cycloalkyl octadecylene group, a cycloalkyl equalizer cyclohexylene group, -C 6 H 10 -CH 2 - group, -C 6 H 10 -C 2 H 4 - group, -C 6 H 10 —C 3 H 6 — group, —C 6 H 10 —C 4 H 8 — group, —C 6 H 10 —C 5 H 10 — group, —C 6 H 10 —C 6 H 12 — group, etc. Among them, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group are included. A methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are more preferable.
　一般式［２－１］のＲ22における炭素数１～６のアルキレン基としては、炭素数１～３のものが好ましく、炭素数２～３のものがより好ましい。また、直鎖状、分枝状及び環状のうちいずれであってもよく、直鎖状が好ましい。具体的には例えば、メチレン基、エチレン基、メチルメチレン基、トリメチレン基、プロピレン基、ジメチルメチレン基、エチルメチレン基、テトラメチレン基、1-メチルトリメチレン基、2-メチルトリメチレン基、1,2-ジメチルエチレン基、1,1-ジメチルエチレン基、エチルエチレン基、エチルメチルメチレン基、プロピルメチレン基、ペンタメチレン基、ヘキサメチレン基、シクロプロピレン基、シクロペンチレン基、シクロヘキシレン基等が挙げられ、中でも、メチレン基、エチレン基、トリメチレン基が好ましく、エチレン基、トリメチレン基がより好ましく、エチレン基が特に好ましい。 The alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1] preferably has 1 to 3 carbon atoms, and more preferably has 2 to 3 carbon atoms. Moreover, any of linear, branched, and cyclic may be sufficient, and linear is preferable. Specifically, for example, methylene group, ethylene group, methylmethylene group, trimethylene group, propylene group, dimethylmethylene group, ethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, hexamethylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, etc. Among them, a methylene group, an ethylene group, and a trimethylene group are preferable, an ethylene group and a trimethylene group are more preferable, and an ethylene group is particularly preferable.
　一般式［２－１］のｂとしては、２～６の整数が好ましく、４～６の整数がより好ましい。ｂが２以上の場合、ｂ個の－(Ｒ22－Ｏ)－基は、それぞれ同一であっても異なっていてもよく、全て同一であるのが好ましい。 As b in the general formula [2-1], an integer of 2 to 6 is preferable, and an integer of 4 to 6 is more preferable. When b is 2 or more, the b — (R 22 —O) — groups may be the same or different, and are preferably all the same.
　一般式［２－１］で示される基の好ましい具体例としては、例えば下記一般式［２－１－１］～［２－１－３］で示される基等が挙げられる。
Figure JPOXMLDOC01-appb-I000125
（式中、ｂは上記と同じ。） Preferable specific examples of the group represented by the general formula [2-1] include groups represented by the following general formulas [2-1-1] to [2-1-3].
Figure JPOXMLDOC01-appb-I000125
(Wherein b is the same as above)
　一般式［２－２］のＲ23及びＲ24における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkylene group having 1 to 6 carbon atoms in R 23 and R 24 of the general formula [2-2] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. The preferred ones are the same.
　一般式［２－２］のｃとしては、２～１３の整数が好ましく、３～８の整数がより好ましい。ｃが２以上の場合、ｃ個の－(Ｒ23－Ｏ)－基は、それぞれ同一であっても異なっていてもよく、全て同一であるのが好ましい。 C in the general formula [2-2] is preferably an integer of 2 to 13, and more preferably an integer of 3 to 8. When c is 2 or more, the c — (R 23 —O) — groups may be the same or different, and are preferably all the same.
　一般式［２－２］で示される基の好ましい具体例としては、例えば下記一般式［２－２－１］～［２－２－３］で示される基等が挙げられ、中でも一般式［２－２－２］で示される基が好ましい。
Figure JPOXMLDOC01-appb-I000126
（式中、ｃは上記と同じ。） Preferable specific examples of the group represented by the general formula [2-2] include groups represented by the following general formulas [2-2-1] to [2-2-3]. 2-2-2] is preferable.
Figure JPOXMLDOC01-appb-I000126
(Where c is the same as above)
　一般式［２］記載の化合物の好ましい具体例としては、下記一般式［２－０１］～［２－１４］記載の化合物等が挙げられ、中でも一般式［２－０９］～［２－１４］記載の化合物が好ましく、一般式［２－１１］及び［２－１２］記載の化合物がより好ましく、一般式［２－１１］記載の化合物が特に好ましい。
Figure JPOXMLDOC01-appb-I000127
（式中、ｂ及びｃは上記と同じであり、ｓは１～６の整数を表し、４～６の整数が好ましく、６がより好ましい。） Preferable specific examples of the compound represented by the general formula [2] include compounds represented by the following general formulas [2-01] to [2-14]. Among them, the general formulas [209] to [2-14] The compounds described in general formulas [2-11] and [2-12] are more preferable, and the compounds described in general formula [2-11] are particularly preferable.
Figure JPOXMLDOC01-appb-I000127
(Wherein b and c are the same as above, s represents an integer of 1 to 6, preferably an integer of 4 to 6, more preferably 6.)
　一般式［３］のＲ27～Ｒ33における炭素数１～３のアルキレン基としては、メチレン基、エチレン基、トリメチレン基等が挙げられ、メチレン基、エチレン基が好ましく、メチレン基がより好ましい。 Examples of the alkylene group having 1 to 3 carbon atoms in R 27 to R 33 in the general formula [3] include a methylene group, an ethylene group, and a trimethylene group. A methylene group and an ethylene group are preferable, and a methylene group is more preferable.
　一般式［３］記載の化合物の好ましい具体例としては、例えば下記式［３－０１］～［３－０３］記載の化合物等が挙げられ、中でも式［３－０１］記載の化合物が好ましい。
Figure JPOXMLDOC01-appb-I000128
Preferable specific examples of the compound represented by the general formula [3] include, for example, compounds represented by the following formulas [3-01] to [3-03], and among them, a compound represented by the formula [3-01] is preferable.
Figure JPOXMLDOC01-appb-I000128
　一般式［４］のＲ34～Ｒ37における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkylene group having 1 to 6 carbon atoms in R 34 to R 37 of the general formula [4] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1], and are preferable. The same is true.
　一般式［４］のｄとしては、１～４の整数が好ましく、１又は２がより好ましい。ｄが２以上の場合、ｄ個の－(Ｏ－Ｒ34)－基は、それぞれ同一であっても異なっていてもよく、全て同一であるのが好ましい。 As d in the general formula [4], an integer of 1 to 4 is preferable, and 1 or 2 is more preferable. When d is 2 or more, the d — (O—R 34 ) — groups may be the same or different, and are preferably the same.
　一般式［４］のｅとしては、０～２の整数が好ましい。ｅが２以上の場合、ｅ個の－(Ｒ35－Ｏ)－基は、それぞれ同一であっても異なっていてもよく、全て同一であるのが好ましい。尚、ｅが０の場合、－(Ｒ35－Ｏ)－は結合手（ボンド）を表す。即ち、隣接する－Ｏ－と－(Ｒ37)g－とが直接結合することを表す。以下、結合手とは同様の意味を表す。 As e in the general formula [4], an integer of 0 to 2 is preferable. When e is 2 or more, the e — (R 35 —O) — groups may be the same or different, and are preferably all the same. When e is 0, — (R 35 —O) — represents a bond. That is, it represents that adjacent —O— and — (R 37 ) g — are directly bonded. Hereinafter, the bond means the same meaning.
　一般式［４］のｆ及びｇは、それぞれ独立して０又は１の整数を表し、ｆとｇが同じであるのが好ましい。尚、ｆが０の場合、－Ｒ36－は結合手を表し、ｇが０の場合、－Ｒ37－は、結合手を表す。 In the general formula [4], f and g each independently represent an integer of 0 or 1, and it is preferable that f and g are the same. When f is 0, —R 36 — represents a bond, and when g is 0, —R 37 — represents a bond.
　一般式［４］記載の化合物の好ましい具体例としては、例えば下記一般式［４－１］又は［４－２］記載の化合物等が挙げられ、中でも一般式［４－１］記載の化合物が好ましい。 Preferable specific examples of the compound represented by the general formula [4] include, for example, the compounds represented by the following general formula [4-1] or [4-2]. Among them, the compounds represented by the general formula [4-1] are exemplified. preferable.
Figure JPOXMLDOC01-appb-I000129
（式中、Ｒ64及びＲ65はそれぞれ独立して、メチレン基、エチレン基又はトリメチレン基を表し、ｄ'は１又は２を表し、ｅ'は０～２の整数を表す。）
Figure JPOXMLDOC01-appb-I000129
(Wherein R 64 and R 65 each independently represents a methylene group, an ethylene group or a trimethylene group, d ′ represents 1 or 2, and e ′ represents an integer of 0 to 2).
Figure JPOXMLDOC01-appb-I000130
（式中、Ｒ66はメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基又はヘキサメチレン基を表し、ｄ''は１～４の整数を表す。）
Figure JPOXMLDOC01-appb-I000130
(Wherein R 66 represents a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group or hexamethylene group, and d ″ represents an integer of 1 to 4)
　一般式［４－１］のＲ64及びＲ65としては、エチレン基が好ましい。 R 64 and R 65 in the general formula [4-1] are preferably ethylene groups.
　一般式［４－１］のｄ'及びｅ'は、同じであるのが好ましい。ｄ'が２の場合、ｄ'個の－(Ｏ－Ｒ64)－基は、同一であっても異なっていてもよく、同一であるのが好ましい。ｅ'が２の場合、ｅ'個の－(Ｒ65－Ｏ)－基は、同一であっても異なっていてもよく、同一であるのが好ましい。尚、ｅ'が０の場合、－(Ｒ65－Ｏ)－は結合手を表す。 In the general formula [4-1], d ′ and e ′ are preferably the same. When d ′ is 2, the d ′ — (O—R 64 ) — groups may be the same or different, and are preferably the same. When e ′ is 2, the e ′ — (R 65 —O) — groups may be the same or different, and are preferably the same. When e ′ is 0, — (R 65 —O) — represents a bond.
　一般式［４－２］のＲ66としては、エチレン基、テトラメチレン基、ヘキサメチレン基が好ましい。 R 66 in the general formula [4-2] is preferably an ethylene group, a tetramethylene group, or a hexamethylene group.
　一般式［４－２］のｄ''としては、１又は２が好ましい。ｄ''が２以上の場合、ｄ''個の－(Ｏ－Ｒ65)－基は、それぞれ同一であっても異なっていてもよく、全て同一であるのが好ましい。 In general formula [4-2], d ″ is preferably 1 or 2. When d ″ is 2 or more, the d ″ number of — (O—R 65 ) — groups may be the same or different, and are preferably all the same.
　一般式［４］記載の化合物のより好ましい具体例としては、例えば下記式［４－０１］～［４－１０］記載の化合物等が挙げられ、中でも式［４－０２］～［４－０５］記載の化合物が好ましい。
Figure JPOXMLDOC01-appb-I000131
More preferred specific examples of the compound represented by the general formula [4] include, for example, compounds represented by the following formulas [4-01] to [4-10], among which the formulas [4-02] to [4-05] The compounds described above are preferred.
Figure JPOXMLDOC01-appb-I000131
　一般式［５］におけるＲ38～Ｒ45のうち、少なくとも２つ以上がビニル基又はビニルケトン基であり、５～８個がビニル基又はビニルケトン基であるものが好ましく、５～７個がビニル基又はビニルケトン基であるものがより好ましい。 Among R 38 to R 45 in the general formula [5], at least two or more are vinyl groups or vinyl ketone groups, preferably 5 to 8 vinyl groups or vinyl ketone groups, and preferably 5 to 7 vinyl groups. Or what is a vinyl ketone group is more preferable.
　一般式［５］記載の化合物の好ましい具体例としては、例えば下記式［５－０１］～［５－０６］記載の化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000132
Preferable specific examples of the compound represented by the general formula [5] include, for example, compounds represented by the following formulas [5-01] to [5-06].
Figure JPOXMLDOC01-appb-I000132
　一般式［６］のＲ46～Ｒ48における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられる。 Examples of the alkylene group having 1 to 6 carbon atoms in R 46 to R 48 of the general formula [6] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1].
　一般式［６］のＲ46及びＲ48としては、メチレン基、エチレン基、トリメチレン基、プロピルメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましく、メチレン基、エチレン基、トリメチレン基がより好ましい。 R 46 and R 48 in the general formula [6] are preferably a methylene group, an ethylene group, a trimethylene group, a propylmethylene group, a pentamethylene group and a hexamethylene group, and more preferably a methylene group, an ethylene group and a trimethylene group.
　一般式［６］のＲ47としては、シクロペンチレン基、シクロヘキシレン基が好ましく、シクロヘキシレン基がより好ましい。 R 47 in the general formula [6] is preferably a cyclopentylene group or a cyclohexylene group, and more preferably a cyclohexylene group.
　一般式［６］記載の化合物の好ましい具体例としては、例えば下記式［６－０１］～［６－０３］記載の化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000133
Preferable specific examples of the compound represented by the general formula [6] include, for example, compounds represented by the following formulas [6-01] to [6-03].
Figure JPOXMLDOC01-appb-I000133
　一般式［７］のＲ49における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、中でもメチレン基、エチレン基が好ましく、メチレン基がより好ましい。 Examples of the alkylene group having 1 to 6 carbon atoms in R 49 of the general formula [7] include the same groups as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. An ethylene group is preferred, and a methylene group is more preferred.
　一般式［７］の環Ar1としては、ベンゼン環が好ましい。 The ring Ar 1 in the general formula [7] is preferably a benzene ring.
　一般式［７］のｈとしては、３～４の整数が好ましい。ｈ個の下記式で示される基は、それぞれ同一であっても異なっていてもよく、全て同一であるのが好ましい。
Figure JPOXMLDOC01-appb-I000134
（式中、Ｒ49は上記と同じ。） As h in the general formula [7], an integer of 3 to 4 is preferable. The h groups represented by the following formulas may be the same or different, and are preferably the same.
Figure JPOXMLDOC01-appb-I000134
(In the formula, R 49 is the same as above.)
　一般式［７］記載の化合物の好ましい具体例としては、例えば下記式［７－０１］～［７－０２］記載の化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000135
Preferable specific examples of the compound represented by the general formula [7] include, for example, compounds represented by the following formulas [7-01] to [7-02].
Figure JPOXMLDOC01-appb-I000135
　一般式［８］の環Ar2及び環Ar3としては、ベンゼン環が好ましい。 As the ring Ar 2 and the ring Ar 3 in the general formula [8], a benzene ring is preferable.
　一般式［８］のＲ50における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、中でもメチレン基、エチレン基、トリメチレン基が好ましく、トリメチレン基がより好ましい。 Examples of the alkylene group having 1 to 6 carbon atoms in R 50 of the general formula [8] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. An ethylene group and a trimethylene group are preferable, and a trimethylene group is more preferable.
　一般式［８］記載の化合物の好ましい具体例としては、例えば下記式［８－０１］～［８－０３］記載の化合物等が挙げられ、中でも式［８－０３］記載の化合物が好ましい。
Figure JPOXMLDOC01-appb-I000136
Preferable specific examples of the compound represented by the general formula [8] include, for example, compounds represented by the following formulas [8-01] to [8-03], and among them, a compound represented by the formula [8-03] is preferable.
Figure JPOXMLDOC01-appb-I000136
　一般式［９］の環Ar4としては、ベンゼン環が好ましい。 The ring Ar 4 in the general formula [9] is preferably a benzene ring.
　一般式［９］記載の化合物の好ましい具体例としては、例えば下記式［９－０１］及び［９－０２］記載の化合物等が挙げられ、中でも式［９－０１］記載の化合物が好ましい。
Figure JPOXMLDOC01-appb-I000137
Preferable specific examples of the compound represented by the general formula [9] include, for example, compounds represented by the following formulas [9-01] and [9-02], and among them, a compound represented by the formula [9-01] is preferable.
Figure JPOXMLDOC01-appb-I000137
　一般式［１０］のｉとしては、０～３の整数が好ましく、０がより好ましい。 I in the general formula [10] is preferably an integer of 0 to 3, more preferably 0.
　一般式［１０］記載の化合物の好ましい具体例としては、例えばジビニルエチレングリコール（1,5-ヘキサジエン-3,4-ジオール）、1,6-ヘプタジエン-3,5-ジオール、1,7-オクタジエン-3,6-ジオール、1,8-ノナジエン-3,7-ジオール等が挙げられ、ジビニルエチレングリコールが好ましい。 Preferable specific examples of the compound represented by the general formula [10] include, for example, divinylethylene glycol (1,5-hexadiene-3,4-diol), 1,6-heptadiene-3,5-diol, 1,7-octadiene. -3,6-diol, 1,8-nonadiene-3,7-diol and the like, and divinylethylene glycol is preferred.
　一般式［１１］のＲ51における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、中でもメチレン基、エチレン基、トリメチレン基が好ましく、メチレン基がより好ましい。 Examples of the alkylene group having 1 to 6 carbon atoms in R 51 of the general formula [11] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. An ethylene group and a trimethylene group are preferable, and a methylene group is more preferable.
　一般式［１１］記載の化合物の好ましい具体例としては、例えばN,N'-メチレンビスアクリルアミド、N,N'-エチレンビスアクリルアミド、N,N'-トリメチレンビスアクリルアミド等が挙げられ、N,N'-メチレンビスアクリルアミドが好ましい。 Preferable specific examples of the compound represented by the general formula [11] include N, N′-methylenebisacrylamide, N, N′-ethylenebisacrylamide, N, N′-trimethylenebisacrylamide and the like. N'-methylenebisacrylamide is preferred.
　一般式［１２］のＲ52における「置換基を有する又は無置換の炭素数１～６のアルキレン基」の炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましい。尚、上記炭素数１～６は、置換基の炭素数を含まない。以下同様に、置換基を有する基の炭素数は、置換基の炭素数を含まないものとする。 The alkylene group having 1 to 6 carbon atoms of the “substituted or unsubstituted alkylene group having 1 to 6 carbon atoms” in R 52 of the general formula [12] is represented by R 22 in the general formula [2-1]. Examples thereof include the same alkylene groups having 1 to 6 carbon atoms, and among them, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable. The above carbon number of 1 to 6 does not include the carbon number of the substituent. Similarly, the number of carbon atoms of a group having a substituent does not include the number of carbon atoms of the substituent.
　一般式［１２］のＲ52における「置換基を有する又は無置換の炭素数６～１０のアリーレン基」の炭素数６～１０のアリーレン基としては、具体的には例えばフェニレン基、ナフチレン基等が挙げられ、フェニレン基が好ましい。 Specific examples of the arylene group having 6 to 10 carbon atoms of the “substituted or unsubstituted arylene group having 6 to 10 carbon atoms” in R 52 of the general formula [12] include, for example, a phenylene group and a naphthylene group. And a phenylene group is preferable.
　一般式［１２］のＲ52における置換基を有する炭素数１～６のアルキレン基及び置換基を有する炭素数６～１０のアリーレン基としては、１又は２個の置換基を有するものが好ましい。その置換基としては、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert－ブチル基、n-ペンチル基、n-ヘキシル基等の炭素数１～６のアルキル基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、tert－ブトキシ基、プロポキシ基、ヘキシルオキシ基等の炭素数１～６のアルコキシ基；フェニル基等の炭素数６～１０のアリール基；ヒドロキシエチル基、ヒドロキシプロピル基等の炭素数１～６のヒドロキシアルキル基；メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基等の炭素数２～７のアルコキシアルキル基；２－ヒドロキシエトキシ基等の炭素数１～６のヒドロキシアルコキシ基；２－メトキシエトキシ基、２－エトキシエトキシ基等の炭素数２～７のアルコキシアルコキシ基；２－スルホエチル基等の炭素数１～６のスルホアルキル基；カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、カルボキシブチル基、カルボキシペンチル基、カルボキシヘキシル基等の炭素数２～７のカルボキシアルキル基；シアノメチル基、シアノエチル基、シアノプロピル基、シアノブチル基、シアノペンチル基、シアノヘキシル基等の炭素数２～７のシアノアルキル基；スルホ基等が挙げられ、炭素数１～６のアルキル基が好ましい。 As the alkylene group having 1 to 6 carbon atoms and the arylene group having 6 to 10 carbon atoms having a substituent in R 52 of the general formula [12], those having 1 or 2 substituents are preferable. Examples of the substituent include 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, and n-hexyl group. An alkyl group of: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, a propoxy group or a hexyloxy group An alkoxy group having 6 to 10 carbon atoms such as a phenyl group; a hydroxyalkyl group having 1 to 6 carbon atoms such as a hydroxyethyl group or a hydroxypropyl group; a methoxyethyl group, an ethoxyethyl group, an ethoxypropyl group, or a butoxyethyl group; An alkoxyalkyl group having 2 to 7 carbon atoms such as a group; a hydroxyalkoxy group having 1 to 6 carbon atoms such as a 2-hydroxyethoxy group; An alkoxyalkoxy group having 2 to 7 carbon atoms such as xoxyethoxy group and 2-ethoxyethoxy group; a sulfoalkyl group having 1 to 6 carbon atoms such as 2-sulfoethyl group; carboxymethyl group, carboxyethyl group, carboxypropyl group, carboxybutyl A carboxyalkyl group having 2 to 7 carbon atoms such as a group, a carboxypentyl group and a carboxyhexyl group; a cyano having 2 to 7 carbon atoms such as a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, a cyanopentyl group and a cyanohexyl group An alkyl group; a sulfo group and the like, and an alkyl group having 1 to 6 carbon atoms is preferable.
　一般式［１２］のＲ52としては、無置換の炭素数１～６のアルキレン基、及び炭素数１～６のアルキル基を置換基として有する又は無置換のフェニレン基が好ましく、直鎖状の炭素数１～６のアルキレン基がより好ましい。 R 52 in the general formula [12] is preferably an unsubstituted alkylene group having 1 to 6 carbon atoms and an unsubstituted phenylene group having an alkyl group having 1 to 6 carbon atoms as a substituent. An alkylene group having 1 to 6 carbon atoms is more preferable.
　一般式［１２－１］及び［１２－２］のＲ53における炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkyl group having 1 to 6 carbon atoms in R 53 of the general formulas [12-1] and [12-2] include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). The preferred ones are the same.
　一般式［１２－１］及び［１２－２］のＲ54、並びに一般式［１２－２］のＲ55における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkylene group having 1 to 6 carbon atoms in R 54 of the general formulas [12-1] and [12-2] and R 55 of the general formula [12-2] include R 22 of the general formula [2-1]. The same as the alkylene group having 1 to 6 carbon atoms in FIG.
　一般式［１２－１］及び［１２－２］の環Ar5としては、ベンゼン環が好ましい。 The ring Ar 5 in the general formulas [12-1] and [12-2] is preferably a benzene ring.
　一般式［１２－１］及び［１２－２］のｊとしては、０又は１が好ましい。ｊが０の場合、環Ar5のベンゼン環又はナフタレン環は置換基を有していないことを意味する。 J in general formulas [12-1] and [12-2] is preferably 0 or 1. When j is 0, it means that the benzene ring or naphthalene ring of the ring Ar 5 has no substituent.
　一般式［１２］記載の化合物の好ましい具体例としては、下記一般式［１２－３］～［１２－６］記載の化合物等が挙げられ、中でも一般式［１２－６］記載の化合物が好ましい。
Figure JPOXMLDOC01-appb-I000138
（式中、Ｒ67は、無置換の炭素数１～６のアルキレン基を表し、Ｒ53～Ｒ55及びｊは、上記と同じ。） Preferable specific examples of the compound represented by the general formula [12] include compounds represented by the following general formulas [12-3] to [12-6], and among them, the compound represented by the general formula [12-6] is preferable. .
Figure JPOXMLDOC01-appb-I000138
(Wherein R 67 represents an unsubstituted alkylene group having 1 to 6 carbon atoms, and R 53 to R 55 and j are the same as described above.)
　一般式［１２－６］のＲ67における無置換の炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましい。 Examples of the unsubstituted alkylene group having 1 to 6 carbon atoms in R 67 of the general formula [12-6] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. Of these, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable.
　一般式［１２－６］記載の化合物の好ましい具体例としては、1,2:4,5-ジエポキシペンタン、1,2:5,6-ジエポキシヘキサン、1,2:6,7-ジエポキシヘプタン、1,2:7,8-ジエポキシオクタン、1,2:8,9-ジエポキシノナン、1,2:9,10-ジエポキシデカン等が挙げられる。 Preferred examples of the compound represented by the general formula [12-6] include 1,2: 4,5-diepoxypentane, 1,2: 5,6-diepoxyhexane, 1,2: 6,7-di- Examples thereof include epoxy heptane, 1,2: 7,8-diepoxyoctane, 1,2: 8,9-diepoxynonane, 1,2: 9,10-diepoxydecane, and the like.
　一般式［１３］のＲ56及びＲ57における「置換基を有する又は無置換の炭素数１～６のアルキル基」の炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkyl group having 1 to 6 carbon atoms of the “substituted or unsubstituted alkyl group having 1 to 6 carbon atoms” in R 56 and R 57 of the general formula [13] include R 4 of the general formula (IV). The same as the alkyl group having 1 to 6 carbon atoms in FIG.
　一般式［１３］のＲ56及びＲ57における「置換基を有する又は無置換の炭素数６～１０のアリール基」の炭素数６～１０のアリール基としては、具体的には例えばフェニル基、ナフチル基等が挙げられ、フェニル基が好ましい。 Specific examples of the aryl group having 6 to 10 carbon atoms of the “substituted or unsubstituted aryl group having 6 to 10 carbon atoms” in R 56 and R 57 of the general formula [13] include a phenyl group, A naphthyl group etc. are mentioned, A phenyl group is preferable.
　一般式［１３］のＲ56及びＲ57における置換基を有する炭素数１～６のアルキル基及び置換基を有する炭素数６～１０のアリール基としては、１～３個の置換基を有するものが好ましく、２個の置換基を有するものがより好ましい。その置換基としては、一般式［１２］のＲ52における「置換基を有する炭素数１～６のアルキレン基及び置換基を有する炭素数６～１０のアリーレン基」の置換基の具体例と同じものが挙げられる。 The alkyl group having 1 to 6 carbon atoms having a substituent and the aryl group having 6 to 10 carbon atoms having a substituent in R 56 and R 57 in the general formula [13] have 1 to 3 substituents Are preferred, and those having two substituents are more preferred. Examples of the substituent are the same as the specific examples of the substituent of R 52 in the general formula [12] “the alkylene group having 1 to 6 carbon atoms having a substituent and the arylene group having 6 to 10 carbon atoms having a substituent”. Things.
　一般式［１３－１］のＲ58における炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkyl group having 1 to 6 carbon atoms in R 58 of the general formula [13-1] include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). It is.
　一般式［１３－１］のＲ59における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられ、好ましいものも同じである。 Examples of the alkylene group having 1 to 6 carbon atoms in R 59 of the general formula [13-1] include the same as the alkylene group having 1 to 6 carbon atoms in R 22 of the general formula [2-1]. Is the same.
　一般式［１３－１］の環Ar6としては、ベンゼン環が好ましい。 The ring Ar 6 in the general formula [13-1] is preferably a benzene ring.
　一般式［１３－１］のｋとしては、１～３の整数が好ましく、２がより好ましい。ｋが０の場合、環Ar6のベンゼン環又はナフタレン環は置換基を有していないことを意味する。 In general formula [13-1], k is preferably an integer of 1 to 3, and more preferably 2. When k is 0, it means that the benzene ring or naphthalene ring of the ring Ar 6 has no substituent.
　一般式［１３］のＲ56及びＲ57としては、Ｒ56とＲ57が同一であるのが好ましく、炭素数１～６のアルキル基を置換基として有する又は無置換のフェニル基、及び一般式［１３－１］で示される基が好ましい。 As R 56 and R 57 in the general formula [13], it is preferable that R 56 and R 57 are the same, a phenyl group having an alkyl group having 1 to 6 carbon atoms as a substituent, or a general formula The group represented by [13-1] is preferred.
　一般式［１３］記載の化合物の好ましい具体例としては、下記一般式［１３－２］及び［１３－３］記載の化合物等が挙げられ、中でも一般式［１３－２］記載の化合物が好ましい。
Figure JPOXMLDOC01-appb-I000139
（式中、Ｒ58、Ｒ59及びｋは、上記と同じであり、２個のＲ58及びＲ59は、それぞれ同一であっても異なっていてもよい。） Preferable specific examples of the compound represented by the general formula [13] include the compounds represented by the following general formulas [13-2] and [13-3], and among them, the compounds represented by the general formula [13-2] are preferable. .
Figure JPOXMLDOC01-appb-I000139
(In the formula, R 58 , R 59 and k are the same as above, and two R 58 and R 59 may be the same or different.)
　一般式［１３－２］記載の化合物の好ましい具体例としては、下記式［１３－０１］～［１３－１２］記載の化合物等が挙げられる。
Figure JPOXMLDOC01-appb-I000140
Preferable specific examples of the compound represented by the general formula [13-2] include compounds represented by the following formulas [13-01] to [13-12].
Figure JPOXMLDOC01-appb-I000140
　一般式［１４］のＲ60における置換基を有する又は無置換の炭素数１～６のアルキレン基、及び置換基を有する又は無置換の炭素数６～１０のアリーレン基としては、一般式［１２］のＲ52におけるそれらと同じものが挙げられる。 Examples of the substituted or unsubstituted alkylene group having 1 to 6 carbon atoms and the substituted or unsubstituted arylene group having 6 to 10 carbon atoms in R 60 of the general formula [14] include those represented by the general formula [12 the same thing can be mentioned as those in R 52 in.
　一般式［１４－１］～［１４－３］のＲ61における炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms in R 61 of the general formulas [14-1] to [14-3] include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). It is done.
　一般式［１４－１］～［１４－３］のＲ62及び一般式［１４－３］のＲ63における炭素数１～６のアルキレン基としては、一般式［２－１］のＲ22における炭素数１～６のアルキレン基と同じものが挙げられる。 The alkylene group having 1 to 6 carbon atoms in R 62 of the general formulas [14-1] to [14-3] and R 63 of the general formula [14-3] is represented by R 22 in the general formula [2-1]. Examples thereof are the same as the alkylene group having 1 to 6 carbon atoms.
　一般式［１４－１］～［１４－３］の環Ar7としては、ベンゼン環が好ましい。 The ring Ar 7 in the general formulas [14-1] to [14-3] is preferably a benzene ring.
　一般式［１４－１］～［１４－３］のｐとしては、０又は１が好ましい。ｐが０の場合、環Ar7のベンゼン環又はナフタレン環は置換基を有していないことを意味する。 In general formulas [14-1] to [14-3], p is preferably 0 or 1. When p is 0, it means that the benzene ring or naphthalene ring of the ring Ar 7 has no substituent.
　一般式［１４］のＲ60としては、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換のフェニレン基が好ましく、無置換の炭素数１～６のアルキレン基、置換基を有するフェニレン基がより好ましく、炭素数１～６のアルキル基を置換基として有するフェニレン基が特に好ましい。 R 60 in the general formula [14] is preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenylene group, and unsubstituted 1 to 6 carbon atoms. An alkylene group and a phenylene group having a substituent are more preferable, and a phenylene group having an alkyl group having 1 to 6 carbon atoms as a substituent is particularly preferable.
　一般式［１４］のｍは、１０～１０００の整数が好ましく、１０～１００の整数がより好ましい。 M in the general formula [14] is preferably an integer of 10 to 1,000, and more preferably an integer of 10 to 100.
　一般式［１４］記載のポリマーの好ましい具体例としては、下記一般式［１４－４］～［１４－８］記載のポリマー等が挙げられ、中でも一般式［１４－５］記載のポリマーが好ましい。
Figure JPOXMLDOC01-appb-I000141
（式中、Ｒ61～Ｒ63、ｐ及びｍは、上記と同じであり、Ｒ68は、無置換の炭素数１～６のアルキレン基を表す。） Preferable specific examples of the polymer represented by the general formula [14] include polymers represented by the following general formulas [14-4] to [14-8], and among them, the polymer represented by the general formula [14-5] is preferable. .
Figure JPOXMLDOC01-appb-I000141
(In the formula, R 61 to R 63 , p and m are the same as above, and R 68 represents an unsubstituted alkylene group having 1 to 6 carbon atoms.)
　一般式［１４－２］のＲ61における無置換の炭素数１～６のアルキレン基としては、一般式［１２－６］のＲ67における無置換の炭素数１～６のアルキレン基と同じものが挙げられ、好ましいものも同じである。 The unsubstituted alkylene group having 1 to 6 carbon atoms in R 61 of the general formula [14-2] is the same as the unsubstituted alkylene group having 1 to 6 carbon atoms in R 67 of the general formula [12-6]. And preferred examples are also the same.
　一般式［１４－５］記載のポリマーの好ましい具体例としては、下記一般式［１４－０１］～［１４－０４］記載のポリマー等が挙げられ、一般式［１４－０１］記載のポリマーが好ましい。
（式中、ｍは上記と同じ。） Preferred specific examples of the polymer represented by the general formula [14-5] include polymers represented by the following general formulas [14-01] to [14-04], and the polymers represented by the general formula [14-01] preferable.
(Wherein m is the same as above)
　本発明に係る架橋剤としては、一般式［２］、［３］、［４］、［９］、［１０］及び［１１］記載の化合物並びに一般式［１４］記載のポリマーが好ましく、一般式［２］、［３］、［４］及び［１０］記載の化合物がより好ましく、一般式［２］及び［４］記載の化合物がさらに好ましく、一般式［２］記載の化合物が特に好ましい。上記架橋剤は、市販のものでも、自体公知の方法によって適宜合成したものでもよい。 As the crosslinking agent according to the present invention, compounds represented by the general formulas [2], [3], [4], [9], [10] and [11] and a polymer represented by the general formula [14] are preferable. The compounds described in the formulas [2], [3], [4] and [10] are more preferable, the compounds described in the general formulas [2] and [4] are more preferable, and the compounds described in the general formula [2] are particularly preferable. . The cross-linking agent may be a commercially available one, or one appropriately synthesized by a method known per se.
［（Ａ）ポリアクリル酸を含む１種以上のポリマーの製造方法］
　（Ａ）ポリアクリル酸を含む１種以上のポリマーは、自体公知の方法に準じて重合反応を行い製造すればよい。例えばポリアクリル酸は、アクリル酸を、要すれば重合開始剤の存在下で、重合反応させることにより製造し得る。 [(A) Method for Producing One or More Polymers Containing Polyacrylic Acid]
(A) One or more polymers containing polyacrylic acid may be produced by performing a polymerization reaction according to a method known per se. For example, polyacrylic acid can be produced by polymerizing acrylic acid, if necessary, in the presence of a polymerization initiator.
　上記重合反応は、自体公知の方法に準じて行えばよく、具体的には、適当な溶媒中、通常３０～２００℃、好ましくは７０～１８０℃、より好ましくは８０～１５０℃で、通常０．１～２４時間、好ましくは１～１０時間反応させればよい。 The polymerization reaction may be carried out according to a method known per se. Specifically, it is usually 30 to 200 ° C., preferably 70 to 180 ° C., more preferably 80 to 150 ° C. in a suitable solvent, usually 0 The reaction may be performed for 1 to 24 hours, preferably 1 to 10 hours.
　上記重合開始剤としては、通常この分野で用いられるものであれば得に限定されず、例えば2,2'-アゾビス(イソブチロニトリル)、2,2'-アゾビス(2,4-ジメチルバレロニトリル)、2,2'-アゾビス(2-メチルプロピオネート)、2,2'-アゾビス(2-メチルブチロニトリル)、過酸化ベンゾイル、過酸化ラウロイル等が挙げられ、中でも2,2'-アゾビス(イソブチロニトリル)が好ましい。これらはそれぞれ単独で用いても、２種以上組み合わせて用いてもよい。該重合開始剤の使用量は、反応物の全量に対して通常０．０１～３０質量％である。 The polymerization initiator is not particularly limited as long as it is usually used in this field. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), benzoyl peroxide, lauroyl peroxide, etc. -Azobis (isobutyronitrile) is preferred. These may be used alone or in combination of two or more. The amount of the polymerization initiator used is usually 0.01 to 30% by mass with respect to the total amount of the reaction product.
　上記溶媒としては、通常この分野で用いられるものであれば得に限定されず、例えばトルエン、1,4-ジオキサン、テトラヒドロフラン、イソプロパノール、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート等が挙げられ、中でもプロピレングリコールモノメチルエーテルアセテートが好ましい。これらはそれぞれ単独で用いても、２種以上組み合わせて用いてもよい。該溶媒の使用量は、反応物の総容量に対して１～１０倍容量である。 The solvent is not particularly limited as long as it is usually used in this field, and examples thereof include toluene, 1,4-dioxane, tetrahydrofuran, isopropanol, methyl ethyl ketone, propylene glycol monomethyl ether acetate and the like, among which propylene glycol monomethyl Ether acetate is preferred. These may be used alone or in combination of two or more. The amount of the solvent used is 1 to 10 times the volume of the total volume of the reaction product.
　上記重合反応後に得られた生成物に対し、必要に応じて、通常この分野で行われる一般的な後処理操作及び精製操作を行ってもよい。具体的には例えば、ろ過、洗浄、抽出、減圧濃縮、再結晶、蒸留、カラムクロマトグラフィ－等を行ってもよい。 The product obtained after the above polymerization reaction may be subjected to general post-treatment operations and purification operations usually performed in this field, if necessary. Specifically, for example, filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, column chromatography and the like may be performed.
　また、（Ａ２）におけるポリアクリル酸以外のポリマーは、所望のポリマーに合わせてモノマーを適宜設定し、上述したポリアクリル酸の重合反応と同様に反応を行い、製造すればよい。
　例えば本発明に係るコポリマーは、上述した重合反応において、アクリル酸の他に、一般式（I）又は一般式（II）で示される化合物１～２種を加えることにより製造し得る。このとき、反応条件（重合開始剤の種類及び使用量、溶媒の種類及び使用量、反応温度、反応時間等）は上述した重合反応と同様にすればよい。 In addition, the polymer other than polyacrylic acid in (A2) may be produced by appropriately setting a monomer in accordance with a desired polymer and performing a reaction in the same manner as the polyacrylic acid polymerization reaction described above.
For example, the copolymer according to the present invention can be produced by adding one or two compounds represented by the general formula (I) or the general formula (II) in addition to acrylic acid in the polymerization reaction described above. At this time, the reaction conditions (type and amount of polymerization initiator, type and amount of solvent, reaction temperature, reaction time, etc.) may be the same as those in the polymerization reaction described above.
　上記本発明に係るコポリマーの重合反応における一般式（I）又は一般式（II）で示される化合物の使用量は、本発明に係るコポリマーにおける、アクリル酸由来のモノマー単位と、一般式（I）又は一般式（II）で示される化合物由来のモノマー単位の質量比となるように適宜設定されればよい。 The amount of the compound represented by the general formula (I) or the general formula (II) used in the polymerization reaction of the copolymer according to the present invention is such that the monomer unit derived from acrylic acid in the copolymer according to the present invention and the general formula (I) Or what is necessary is just to set suitably so that it may become a mass ratio of the monomer unit derived from the compound shown by general formula (II).
　（Ａ）ポリアクリル酸を含む１種以上のポリマーを中和する場合には、自体公知の方法に準じて中和すればよい。例えば、（Ａ）ポリアクリル酸を含む１種以上のポリマーのうちカルボキシ基を有するポリマーに、該ポリマー中のカルボキシ基１molに対して水酸化ナトリウム等のアルカリ金属０．５～１molを添加し、中和すればよい。中和するポリマーは架橋しているものであってもよく、中和後に架橋するものでもよい。中和する際に用いられる溶媒としては、上述した重合反応において用いられる溶媒と同じものが挙げられる。 (A) When neutralizing one or more polymers including polyacrylic acid, it may be neutralized according to a method known per se. For example, (A) 0.5 to 1 mol of an alkali metal such as sodium hydroxide is added to 1 mol of a carboxy group in one or more kinds of polymers containing polyacrylic acid with respect to 1 mol of the carboxy group in the polymer, Neutralize. The polymer to be neutralized may be crosslinked or may be crosslinked after neutralization. Examples of the solvent used for neutralization include the same solvents as those used in the polymerization reaction described above.
　（Ａ）ポリアクリル酸を含む１種以上のポリマーを架橋する場合には、本発明に係る架橋剤を用いて、自体公知の方法に準じて架橋すればよい。
　例えば、上述した重合反応においてさらに一般式［１］～［１１］記載の化合物から選ばれる架橋剤を加えることにより、重合反応と架橋反応を同時に行えばよい。或いは、上述した重合反応の後に、得られたポリマーと、一般式［１２］もしくは［１３］記載の化合物又は一般式［１４］記載のポリマーとを、上述した重合反応と同様の反応条件（溶媒の種類及び使用量、反応温度、反応時間等）で架橋反応を行えばよい。 (A) When one or more polymers containing polyacrylic acid are cross-linked, the cross-linking agent according to the present invention may be used according to a method known per se.
For example, the polymerization reaction and the crosslinking reaction may be performed simultaneously by adding a crosslinking agent selected from the compounds described in the general formulas [1] to [11] in the polymerization reaction described above. Alternatively, after the polymerization reaction described above, the obtained polymer and the compound represented by the general formula [12] or [13] or the polymer represented by the general formula [14] are reacted under the same reaction conditions (solvents) as the polymerization reaction described above. And the amount used, reaction temperature, reaction time, etc.).
　一般式［１］～［１１］記載の化合物の使用量は、使用するモノマー１molに対して、通常０．００１～１０mol％、好ましくは０．００５～１mol％、より好ましくは０．０１～０．５mol％である。
　一般式［１２］もしくは［１３］記載の化合物又は一般式［１４］記載のポリマーの使用量は、架橋対象であるポリマーの質量に対して、通常０．０１～４０質量％、好ましくは０．０５～２０質量％、より好ましくは０．１～１０質量％である。 The amount of the compounds represented by the general formulas [1] to [11] is usually 0.001 to 10 mol%, preferably 0.005 to 1 mol%, more preferably 0.01 to 0, based on 1 mol of the monomer used. .5 mol%.
The amount of the compound represented by the general formula [12] or [13] or the polymer represented by the general formula [14] is usually 0.01 to 40% by mass, preferably 0.8%, based on the mass of the polymer to be crosslinked. 05 to 20% by mass, more preferably 0.1 to 10% by mass.
　架橋されたポリアクリル酸は、具体的には以下の如く調製される。
　即ち、アクリル酸と、アクリル酸１molに対して０．０１～０．５mol％の一般式［１］～［１１］記載の化合物から選ばれる架橋剤とを、2,2'-アゾビス(イソブチロニトリル)等の重合開始剤の存在下、総容量に対して１～１０倍容量のプロピレングリコールモノメチルエーテルアセテート等の溶媒に、溶解又は分散させる。その後、８０～１５０℃で０．１～１０時間重合反応及び架橋反応させ、架橋されたポリアクリル酸を調製する。また、要すれば、得られた架橋されたポリアクリル酸のカルボキシ基１molに対して０．５～１molの水酸化ナトリウム等のアルカリ金属を添加し、架橋されたポリアクリル酸塩としてもよい。
　或いは、重量平均分子量10,000～5,000,000のポリアクリル酸と、ポリアクリル酸の質量に対して０．１～１０質量％の一般式［１２］もしくは［１３］記載の化合物又は一般式［１４］記載のポリマーとを、総容量に対して１～１０倍容量のプロピレングリコールモノメチルエーテルアセテート等の溶媒に、溶解又は分散させる。その後、８０～１５０℃で０．１～１０時間架橋反応させ、架橋されたポリアクリル酸を調製する。また、要すれば、得られた架橋されたポリアクリル酸のカルボキシ基１molに対して０．５～１molの水酸化ナトリウム等のアルカリ金属を添加し、架橋されたポリアクリル酸塩としてもよい。 Specifically, the cross-linked polyacrylic acid is prepared as follows.
That is, 2,2′-azobis (isobutyric acid) and acrylic acid and 0.01 to 0.5 mol% of a crosslinking agent selected from the compounds represented by the general formulas [1] to [11] with respect to 1 mol of acrylic acid. In the presence of a polymerization initiator such as (ronitrile), it is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a polymerization reaction and a crosslinking reaction are carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked polyacrylic acid. Further, if necessary, 0.5-1 mol of an alkali metal such as sodium hydroxide may be added to 1 mol of the carboxy group of the obtained crosslinked polyacrylic acid to form a crosslinked polyacrylate.
Alternatively, a polyacrylic acid having a weight average molecular weight of 10,000 to 5,000,000 and a compound represented by the general formula [12] or [13] or 0.1 to 10% by mass relative to the mass of the polyacrylic acid or the general formula [14] The polymer is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a crosslinking reaction is carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked polyacrylic acid. Further, if necessary, 0.5-1 mol of an alkali metal such as sodium hydroxide may be added to 1 mol of the carboxy group of the obtained crosslinked polyacrylic acid to form a crosslinked polyacrylate.
　架橋された本発明に係るコポリマーは、具体的には以下の如く調製される。
　即ち、アクリル酸と、アクリル酸３０～７０質量部に対して７０～３０質量部の一般式（I）又は一般式（II）で示される化合物１～２種と、使用するモノマー１molに対して０．０１～０．５mol％の一般式［１］～［１１］記載の化合物から選ばれる架橋剤とを、2,2'-アゾビス(イソブチロニトリル)等の重合開始剤の存在下、総容量に対して１～１０倍容量のプロピレングリコールモノメチルエーテルアセテート等の溶媒に、溶解又は分散させる。その後、８０～１５０℃で０．１～１０時間重合反応及び架橋反応させ、架橋された本発明に係るコポリマーを調製する。また、要すれば、得られた架橋された本発明に係るコポリマーのカルボキシ基１molに対して０．５～１molの水酸化ナトリウム等のアルカリ金属を添加し、架橋された本発明に係るコポリマー塩としてもよい。
　或いは、アクリル酸と、アクリル酸３０～７０質量部に対して７０～３０質量部の一般式（I）又は一般式（II）で示される化合物１～２種とを、2,2'-アゾビス(イソブチロニトリル)等の重合開始剤の存在下、総容量に対して１～１０倍容量のプロピレングリコールモノメチルエーテルアセテート等の溶媒に、溶解又は分散させる。その後、８０～１５０℃で０．１～１０時間重合反応させ、本発明に係るコポリマーを調製する。次いで、得られた本発明に係るコポリマーと、コポリマーの質量に対して０．１～１０質量％の一般式［１２］もしくは［１３］記載の化合物又は一般式［１４］記載のポリマーとを、総容量に対して１～１０倍容量のプロピレングリコールモノメチルエーテルアセテート等の溶媒中に、溶解又は分散させる。その後、８０～１５０℃で、０．１～１０時間架橋反応させ、架橋された本発明に係るコポリマーを調製する。また、要すれば、得られた架橋された本発明に係るコポリマーのカルボキシ基１molに対して０．５～１molの水酸化ナトリウム等のアルカリ金属を添加し、架橋された本発明に係るコポリマー塩としてもよい。 The crosslinked copolymer according to the present invention is specifically prepared as follows.
That is, with respect to acrylic acid, 70 to 30 parts by mass of the compound represented by the general formula (I) or general formula (II) with respect to 30 to 70 parts by mass of acrylic acid, and 1 mol of the monomer used. 0.01 to 0.5 mol% of a crosslinking agent selected from the compounds represented by the general formulas [1] to [11] in the presence of a polymerization initiator such as 2,2′-azobis (isobutyronitrile), It is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a polymerization reaction and a crosslinking reaction are carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked copolymer according to the present invention. In addition, if necessary, 0.5 to 1 mol of an alkali metal such as sodium hydroxide is added to 1 mol of the carboxy group of the obtained cross-linked copolymer according to the present invention to cross-link the copolymer salt according to the present invention. It is good.
Alternatively, acrylic acid and 70 to 30 parts by mass of the compound represented by the general formula (I) or the general formula (II) with respect to 30 to 70 parts by mass of acrylic acid are combined with 2,2′-azobis. In the presence of a polymerization initiator such as (isobutyronitrile), it is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a polymerization reaction is carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a copolymer according to the present invention. Next, the obtained copolymer according to the present invention and 0.1 to 10% by mass of the compound of the general formula [12] or [13] or the polymer of the general formula [14] with respect to the mass of the copolymer, It is dissolved or dispersed in a solvent such as propylene glycol monomethyl ether acetate having a volume of 1 to 10 times the total volume. Thereafter, a crosslinking reaction is carried out at 80 to 150 ° C. for 0.1 to 10 hours to prepare a crosslinked copolymer according to the present invention. In addition, if necessary, 0.5 to 1 mol of an alkali metal such as sodium hydroxide is added to 1 mol of the carboxy group of the obtained cross-linked copolymer according to the present invention to cross-link the copolymer salt according to the present invention. It is good.
［（Ｂ）２価～１０価のアルコール］
　本発明の結着剤組成物における（Ｂ）２価～１０価のアルコール（以下、本発明に係るアルコールと略記する場合がある）としては、通常この分野で用いられる従来公知のアルコールであればよく、２価～６価のものが好ましく、２価～４価のものがより好ましい。 [(B) Divalent to 10-valent alcohol]
In the binder composition of the present invention, the (B) divalent to 10-valent alcohol (hereinafter sometimes abbreviated as the alcohol according to the present invention) is a conventionally known alcohol that is usually used in this field. The divalent to hexavalent ones are preferable, and the divalent to tetravalent ones are more preferable.
　本発明に係るアルコールの具体例としては、例えば下記一般式（Ｂ１）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000143
（式中、Ｒ71は、炭素数１～６のアルキレン基を表し、Ｒ72は、ヒドロキシ基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ73は、水素原子、炭素数１～６のアルキル基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ74は、－Ｏ－を鎖中に有していてもよい炭素数１～６のアルキレン基を表し、ｒは０～４の整数を表す。ただし、複数のＲ72、複数のＲ73及び複数のＲ74は、それぞれ同一であっても異なっていてもよい。） Specific examples of the alcohol according to the present invention include compounds represented by the following general formula (B1).
Figure JPOXMLDOC01-appb-I000143
Wherein R 71 represents an alkylene group having 1 to 6 carbon atoms, R 72 represents a hydroxy group or a hydroxyalkyl group having 1 to 6 carbon atoms, R 73 represents a hydrogen atom, 1 to 6 carbon atoms Or an alkyl group having 1 to 6 carbon atoms, R 74 represents an alkylene group having 1 to 6 carbon atoms which may have —O— in the chain, and r represents 0 to 4 carbon atoms. Represents an integer, provided that the plurality of R 72 , the plurality of R 73 and the plurality of R 74 may be the same or different.
　一般式（Ｂ１）のＲ71における炭素数１～６のアルキレン基としては、ｒが０の場合、炭素数３～６のものが好ましく、ｒが１～４の整数の場合、炭素数１～４のものが好ましい。また、直鎖状、分枝状及び環状のうちいずれであってもよく、直鎖状及び分枝状のものが好ましく、直鎖状のものがより好ましい。具体的には例えば、メチレン基、エチレン基、メチルメチレン基、トリメチレン基、プロピレン基、ジメチルメチレン基、エチルメチレン基、テトラメチレン基、1-メチルトリメチレン基、2-メチルトリメチレン基、1,2-ジメチルエチレン基、1,1-ジメチルエチレン基、エチルエチレン基、エチルメチルメチレン基、プロピルメチレン基、ペンタメチレン基、ヘキサメチレン基、シクロプロピレン基、シクロペンチレン基、シクロヘキシレン基等が挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましい。ｒが０の場合、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基がより好ましく、ｒが１～４の整数の場合、メチレン基、エチレン基、トリメチレン基、テトラメチレン基がより好ましい。 The alkylene group having 1 to 6 carbon atoms in R 71 of the general formula (B1) is preferably one having 3 to 6 carbon atoms when r is 0, and one having 1 to 6 carbon atoms when r is an integer of 1 to 4. 4 is preferred. Moreover, it may be any of linear, branched and cyclic, preferably linear and branched, and more preferably linear. Specifically, for example, methylene group, ethylene group, methylmethylene group, trimethylene group, propylene group, dimethylmethylene group, ethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, hexamethylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, etc. Among these, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable. When r is 0, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are more preferable, and when r is an integer of 1 to 4, a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are more preferable.
　一般式（Ｂ１）のＲ72及びＲ73における炭素数１～６のヒドロキシアルキル基としては、一般式（II）のＲ13における炭素数１～６のヒドロキシアルキル基と同じものが挙げられ、中でもヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基が好ましく、ヒドロキシメチル基、ヒドロキシエチル基がより好ましい。 Examples of the hydroxyalkyl group having 1 to 6 carbon atoms in R 72 and R 73 of the general formula (B1) include the same as the hydroxyalkyl group having 1 to 6 carbon atoms in R 13 of the general formula (II). A hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, and a hydroxymethyl group and a hydroxyethyl group are more preferable.
　一般式（Ｂ１）のＲ73における炭素数１～６のアルキル基としては、一般式（IV）のＲ4における炭素数１～６のアルキル基と同じものが挙げられ、中でもメチル基、エチル基、n-プロピル基、n-ブチル基が好ましく、メチル基、エチル基がより好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms in R 73 of the general formula (B1) include the same as the alkyl group having 1 to 6 carbon atoms in R 4 of the general formula (IV). N-propyl group and n-butyl group are preferable, and methyl group and ethyl group are more preferable.
　一般式（Ｂ１）のＲ74における－Ｏ－を鎖中に有さない炭素数１～６のアルキレン基としては、一般式（Ｂ１）のＲ71における炭素数１～６のアルキレン基と同じものが挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましく、メチレン基、エチレン基、トリメチレン基、テトラメチレン基がより好ましく、メチレン基、エチレン基が特に好ましい。 The alkylene group having 1 to 6 carbon atoms which does not have —O— in the chain in R 74 of the general formula (B1) is the same as the alkylene group having 1 to 6 carbon atoms in R 71 of the general formula (B1). Among them, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable, a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are more preferable, and a methylene group and an ethylene group are preferable. Particularly preferred.
　一般式（Ｂ１）のＲ74における－Ｏ－を鎖中に有する炭素数１～６のアルキレン基としては、例えば下記一般式（Ｂ１－１）で示される基等が挙げられる。 Examples of the alkylene group having 1 to 6 carbon atoms and having —O— in the chain of R 74 in the general formula (B1) include groups represented by the following general formula (B1-1).
－(Ｒ75－Ｏ－)ｔ－Ｒ76－　　　（Ｂ１－１）
（式中、Ｒ75及びＲ76はそれぞれ独立して、直鎖状又は分枝状の炭素数１～５のアルキレン基を表し、ｔは、１～５の整数を表す。ただし、式中の炭素数の総数は２～６であり、ｔ個のＲ75はそれぞれ同一であっても異なっていてもよい。） - (R 75 -O-) t -R 76 - (B1-1)
(In the formula, R 75 and R 76 each independently represents a linear or branched alkylene group having 1 to 5 carbon atoms, and t represents an integer of 1 to 5, provided that The total number of carbon atoms is 2 to 6, and t R75s may be the same or different.
　一般式（Ｂ１－１）のＲ75及びＲ76における炭素数１～５のアルキレン基としては、炭素数１～３のものが好ましい。また、直鎖状又は分枝状のいずれであってもよく、直鎖状のものがより好ましい。具体的には例えば、メチレン基、エチレン基、メチルメチレン基、トリメチレン基、プロピレン基、ジメチルメチレン基、エチルメチレン基、テトラメチレン基、1-メチルトリメチレン基、2-メチルトリメチレン基、1,2-ジメチルエチレン基、1,1-ジメチルエチレン基、エチルエチレン基、エチルメチルメチレン基、プロピルメチレン基、ペンタメチレン基等が挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基が好ましく、メチレン基、エチレン基がより好ましい。 As the alkylene group having 1 to 5 carbon atoms in R 75 and R 76 in the general formula (B1-1), those having 1 to 3 carbon atoms are preferable. Moreover, either linear or branched may be sufficient and a linear thing is more preferable. Specifically, for example, methylene group, ethylene group, methylmethylene group, trimethylene group, propylene group, dimethylmethylene group, ethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples include 2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, etc. Among them, methylene group, ethylene group, trimethylene group, tetramethylene group, pentane group, etc. A methylene group is preferable, and a methylene group and an ethylene group are more preferable.
　一般式（Ｂ１－１）のｔとしては、１又は２が好ましく、１がより好ましい。 As t in the general formula (B1-1), 1 or 2 is preferable, and 1 is more preferable.
　一般式（Ｂ１－１）で示される基の好ましい具体例としては、下記一般式（Ｂ１－２）で示される基が挙げられる。 Preferred specific examples of the group represented by the general formula (B1-1) include a group represented by the following general formula (B1-2).
－Ｒ75'－Ｏ－Ｒ76'－　　　（Ｂ１－２）
（式中、Ｒ75'及びＲ76'はそれぞれ独立して、直鎖状の炭素数１～５のアルキレン基を表す。ただし、式中の炭素数の総数は２～６である。） -R 75 '-O-R 76 '-(B1-2)
(Wherein R 75 ′ and R 76 ′ each independently represents a linear alkylene group having 1 to 5 carbon atoms, provided that the total number of carbon atoms in the formula is 2 to 6).
　一般式（Ｂ１－２）のＲ75'及びＲ76'における直鎖状の炭素数１～５のアルキレン基としては、具体的にはメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基が挙げられ、中でもメチレン基、エチレン基が好ましい。 Specific examples of the linear alkylene group having 1 to 5 carbon atoms in R 75 ′ and R 76 ′ of the general formula (B1-2) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. A methylene group and an ethylene group are preferable.
　一般式（Ｂ１－２）で示される基としては、具体的には例えば
-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2-O-CH2CH2CH2-、
-CH2-O-CH2CH2CH2CH2-、-CH2-O-CH2CH2CH2CH2CH2-、
-CH2CH2-O-CH2-、-CH2CH2-O-CH2CH2-、-CH2CH2-O-CH2CH2CH2-、-CH2CH2-O-CH2CH2CH2CH2-、
-CH2CH2CH2-O-CH2-、-CH2CH2CH2-O-CH2CH2-、-CH2CH2CH2-O-CH2CH2CH2-、
-CH2CH2CH2CH2-O-CH2-、-CH2CH2CH2CH2-O-CH2CH2-、-CH2CH2CH2CH2CH2-O-CH2-、
等が挙げられ、中でも
-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-CH2-、-CH2CH2-O-CH2CH2-
が好ましく、
-CH2-O-CH2-、-CH2CH2-O-CH2CH2-がより好ましく、-CH2-O-CH2-が特に好ましい。 Specific examples of the group represented by the general formula (B1-2) include
-CH 2 -O-CH 2- , -CH 2 -O-CH 2 CH 2- , -CH 2 -O-CH 2 CH 2 CH 2- ,
-CH 2 -O-CH 2 CH 2 CH 2 CH 2- , -CH 2 -O-CH 2 CH 2 CH 2 CH 2 CH 2- ,
-CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 -O-CH 2 CH 2 CH 2- , -CH 2 CH 2 -O- CH 2 CH 2 CH 2 CH 2- ,
-CH 2 CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2- ,
-CH 2 CH 2 CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 CH 2 CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2 CH 2 -O-CH 2 -,
Etc., among others
-CH 2 -O-CH 2- , -CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2-
Is preferred,
—CH 2 —O—CH 2 — and —CH 2 CH 2 —O—CH 2 CH 2 — are more preferred, and —CH 2 —O—CH 2 — is particularly preferred.
　一般式（Ｂ１）のＲ72としては、ヒドロキシ基及び直鎖状の炭素数１～６のヒドロキシアルキル基が好ましく、ヒドロキシ基及び末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基がより好ましく、末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基が特に好ましい。具体的にはヒドロキシ基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基が好ましく、ヒドロキシ基、ヒドロキシメチル基、ヒドロキシエチル基がより好ましく、ヒドロキシメチル基、ヒドロキシエチル基が特に好ましい。 As R 72 in the general formula (B1), a hydroxy group and a linear hydroxyalkyl group having 1 to 6 carbon atoms are preferable, and a linear group in which a hydroxy group and one hydrogen at a terminal portion are substituted with a hydroxy group are used. And a straight-chain hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen atom in the terminal portion is substituted with a hydroxy group is particularly preferable. Specifically, a hydroxy group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, a hydroxy group, a hydroxymethyl group, and a hydroxyethyl group are more preferable, and a hydroxymethyl group and a hydroxyethyl group are particularly preferable.
　一般式（Ｂ１）のＲ73としては、水素原子、直鎖状の炭素数１～６のアルキル基及び直鎖状の炭素数１～６のヒドロキシアルキル基が好ましく、水素原子、直鎖状の炭素数１～６のアルキル基及び末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基がより好ましく、末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基が特に好ましい。具体的には水素原子、メチル基、エチル基、n-プロピル基、n-ブチル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基が好ましく、水素原子、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基がより好ましく、ヒドロキシメチル基、ヒドロキシエチル基が特に好ましい。 R 73 in formula (B1) is preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a linear hydroxyalkyl group having 1 to 6 carbon atoms. A linear alkylalkyl group having 1 to 6 carbon atoms in which an alkyl group having 1 to 6 carbon atoms and one hydrogen at a terminal portion are substituted with a hydroxy group is more preferable, and one hydrogen at a terminal portion is a hydroxy group. A straight-chain C1-C6 hydroxyalkyl group substituted with is particularly preferred. Specifically, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, and a hydrogen atom, a methyl group, an ethyl group, A hydroxymethyl group and a hydroxyethyl group are more preferable, and a hydroxymethyl group and a hydroxyethyl group are particularly preferable.
　一般式（Ｂ１）のＲ74としては、直鎖状又は分枝状の炭素数１～６のアルキレン基及び一般式（Ｂ１－１）で示される基が好ましく、直鎖状の炭素数１～６のアルキレン基及び一般式（Ｂ１－２）で示される基がより好ましく、直鎖状の炭素数１～６のアルキレン基が特に好ましい。具体的にはメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、
-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-CH2-、-CH2CH2-O-CH2CH2-
が好ましく、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、
-CH2-O-CH2-、-CH2CH2-O-CH2CH2-
がより好ましく、メチレン基、エチレン基、-CH2-O-CH2-がさらに好ましく、
メチレン基、エチレン基が特に好ましい。 R 74 in the general formula (B1) is preferably a linear or branched alkylene group having 1 to 6 carbon atoms and a group represented by the general formula (B1-1). The alkylene group of 6 and the group represented by the general formula (B1-2) are more preferable, and a linear alkylene group having 1 to 6 carbon atoms is particularly preferable. Specifically, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group,
-CH 2 -O-CH 2- , -CH 2 -O-CH 2 CH 2- , -CH 2 CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2-
Are preferred, methylene group, ethylene group, trimethylene group, tetramethylene group,
-CH 2 -O-CH 2- , -CH 2 CH 2 -O-CH 2 CH 2-
Is more preferable, methylene group, ethylene group, -CH 2 -O-CH 2 -is more preferable,
A methylene group and an ethylene group are particularly preferable.
　一般式（Ｂ１）のｒとしては、０～２の整数が好ましく、０又は１がより好ましい。 R in the general formula (B1) is preferably an integer of 0 to 2, more preferably 0 or 1.
　一般式（Ｂ１）で示される化合物の好ましい具体例としては、下記一般式（Ｂ２）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000144
（式中、Ｒ71～Ｒ73、Ｒ75、Ｒ76及びｔは、上記と同じであり、Ｒ77は、直鎖状又は分枝状の炭素数１～６のアルキレン基を表し、ｒ2は０又は１を表し、ｒ2が０のときｒ1は０を表し、ｒ2が１のときｒ1は０～３の整数を表す。ただし、複数のＲ72、Ｒ73、Ｒ75、Ｒ76及びｔは、それぞれ同一であっても異なっていてもよい。） Preferable specific examples of the compound represented by the general formula (B1) include a compound represented by the following general formula (B2).
Figure JPOXMLDOC01-appb-I000144
(Wherein, R 71 ~ R 73, R 75, R 76 and t are as defined above, R 77 represents a linear or branched alkylene group having 1 to 6 carbon atoms, r 2 represents 0 or 1, represents r 1 is 0 when r 2 is 0, r 1 when r 2 is 1 represents an integer of 0-3. However, a plurality of R 72, R 73, R 75 , R 76 and t may be the same or different.)
　一般式（Ｂ２）のＲ77における直鎖状又は分枝状の炭素数１～６のアルキレン基としては、一般式（Ｂ１）のＲ71における炭素数１～６のアルキレン基の具体例のうち直鎖状又は分枝状のものが挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましく、メチレン基、エチレン基、トリメチレン基、テトラメチレン基がより好ましく、メチレン基、エチレン基が特に好ましい。 Examples of the linear or branched alkylene group having 1 to 6 carbon atoms in R 77 of the general formula (B2) include specific examples of the alkylene group having 1 to 6 carbon atoms in R 71 of the general formula (B1). Examples include straight-chain or branched ones. Among them, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable, and a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are preferable. More preferred are a methylene group and an ethylene group.
　一般式（Ｂ２）のｒ2としては、０又は１が好ましい。 As r < 2 > of general formula (B2), 0 or 1 is preferable.
　一般式（Ｂ２）で示される化合物の好ましい具体例としては、下記一般式（Ｂ３）～（Ｂ５）で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000145
（式中、Ｒ75'及びＲ76'は、上記と同じであり、Ｒ71'及びＲ77'は、直鎖状の炭素数１～６のアルキレン基を表し、Ｒ72'は、ヒドロキシ基又は末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基を表し、Ｒ73'は、水素原子、直鎖状の炭素数１～６のアルキル基又は末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基を表し、ｒ3は、１～３の整数を表す。ただし、Ｒ75'及びＲ76'の炭素数の総数は２～６であり、複数のＲ72'、Ｒ73'、Ｒ75'及びＲ76'はそれぞれ同一であっても異なっていてもよい。） Preferable specific examples of the compound represented by the general formula (B2) include compounds represented by the following general formulas (B3) to (B5).
Figure JPOXMLDOC01-appb-I000145
Wherein R 75 ′ and R 76 ′ are the same as above, R 71 ′ and R 77 ′ represent a linear alkylene group having 1 to 6 carbon atoms, and R 72 ′ represents a hydroxy group Or a linear hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen atom in the terminal portion is substituted with a hydroxy group, and R 73 ′ represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms Represents a straight-chain hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen in a group or a terminal portion is substituted with a hydroxy group, and r 3 represents an integer of 1 to 3, provided that R 75 ′ and The total number of carbon atoms of R 76 ′ is 2 to 6, and a plurality of R 72 ′, R 73 ′, R 75 ′ and R 76 ′ may be the same or different.
　一般式（Ｂ３）～（Ｂ５）のＲ71'における直鎖状の炭素数１～６のアルキレン基としては、具体的にはメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が挙げられる。一般式（Ｂ３）においては、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が好ましく、一般式（Ｂ４）においては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基が好ましく、一般式（Ｂ５）においては、メチレン基、エチレン基が好ましい。 Specific examples of the linear alkylene group having 1 to 6 carbon atoms in R 71 ′ of the general formulas (B3) to (B5) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, A hexamethylene group is mentioned. In general formula (B3), trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group are preferable. In general formula (B4), methylene group, ethylene group, trimethylene group and tetramethylene group are preferable. In (B5), a methylene group and an ethylene group are preferable.
　一般式（Ｂ４）及び（Ｂ５）のＲ77'における直鎖状の炭素数１～６のアルキレン基としては、具体的にはメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が挙げられ、中でもメチレン基、エチレン基、トリメチレン基、テトラメチレン基が好ましく、メチレン基、エチレン基がより好ましい。 Specific examples of the linear alkylene group having 1 to 6 carbon atoms in R 77 ′ of the general formulas (B4) and (B5) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, A hexamethylene group can be mentioned, among which a methylene group, an ethylene group, a trimethylene group and a tetramethylene group are preferable, and a methylene group and an ethylene group are more preferable.
　一般式（Ｂ４）及び（Ｂ５）のＲ72'及びＲ73'における末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基としては、具体的にはヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシヘキシル基が挙げられ、中でもヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基が好ましく、ヒドロキシメチル基、ヒドロキシエチル基がより好ましい。 Examples of the linear hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen at a terminal portion in R 72 ′ and R 73 ′ in the general formulas (B4) and (B5) is substituted with a hydroxy group include Include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, and hydroxyhexyl group. Among them, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, and hydroxybutyl group are preferable. And a hydroxyethyl group is more preferable.
　一般式（Ｂ４）及び（Ｂ５）のＲ73'における直鎖状の炭素数１～６のアルキル基としては、具体的にはメチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基が挙げられ、中でもメチル基、エチル基、n-プロピル基、n-ブチル基が好ましく、メチル基、エチル基がより好ましい。 Specific examples of the linear alkyl group having 1 to 6 carbon atoms in R 73 ′ of the general formulas (B4) and (B5) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n -Pentyl group and n-hexyl group can be mentioned, among which methyl group, ethyl group, n-propyl group and n-butyl group are preferable, and methyl group and ethyl group are more preferable.
　一般式（Ｂ４）のＲ72'としては、ヒドロキシ基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基が好ましく、ヒドロキシ基、ヒドロキシメチル基、ヒドロキシエチル基がより好ましく、ヒドロキシメチル基、ヒドロキシエチル基が特に好ましい。 R 72 ′ in formula (B4) is preferably a hydroxy group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group, more preferably a hydroxy group, a hydroxymethyl group or a hydroxyethyl group, and a hydroxymethyl group A hydroxyethyl group is particularly preferred.
　一般式（Ｂ４）のＲ73'としては、水素原子、メチル基、エチル基、n-プロピル基、n-ブチル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基が好ましく、水素原子、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基がより好ましく、ヒドロキシメチル基、ヒドロキシエチル基が特に好ましい。 R 73 ′ in the general formula (B4) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, or a hydroxybutyl group. An atom, a methyl group, an ethyl group, a hydroxymethyl group, and a hydroxyethyl group are more preferable, and a hydroxymethyl group and a hydroxyethyl group are particularly preferable.
　一般式（Ｂ５）のＲ72'及びＲ73'としては、末端部分の１個の水素がヒドロキシ基で置換された直鎖状の炭素数１～６のヒドロキシアルキル基が好ましく、具体的にはヒドロキシメチル基、ヒドロキシエチル基が好ましい。 As R 72 ′ and R 73 ′ in the general formula (B5), a linear hydroxyalkyl group having 1 to 6 carbon atoms in which one hydrogen at a terminal portion is substituted with a hydroxy group is preferable. A hydroxymethyl group and a hydroxyethyl group are preferred.
　一般式（Ｂ５）のｒ3としては、１が好ましい。 As r < 3 > of general formula (B5), 1 is preferable.
　一般式（Ｂ３）で示される化合物の好ましい具体例としては、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオールが挙げられる。 Preferred specific examples of the compound represented by the general formula (B3) include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
　一般式（Ｂ４）で示される化合物の好ましい具体例としては、下記式で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000146
Preferable specific examples of the compound represented by the general formula (B4) include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-I000146
　下記具体例の中でも、1,2,4-ブタントリオール、1,2,5-ペンタントリオール、1,2,6-ヘキサントリオール、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトールが好ましく、1,2,6-ヘキサントリオール、トリメチロールプロパン、ペンタエリスリトールがより好ましく、ペンタエリスリトールが特に好ましい。 Among the following specific examples, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, and pentaerythritol are preferable. 6-hexanetriol, trimethylolpropane, and pentaerythritol are more preferable, and pentaerythritol is particularly preferable.
　一般式（Ｂ５）で示される化合物の好ましい具体例としては、ジペンタエリスリトール、トリペンタエリスリトール、テトラペンタエリスリトールが挙げられ、ジペンタエリスリトールが好ましい。 Specific examples of the compound represented by the general formula (B5) include dipentaerythritol, tripentaerythritol, and tetrapentaerythritol, and dipentaerythritol is preferable.
　本発明に係るアルコールとしては、一般式（Ｂ３）～（Ｂ５）で示される化合物の好ましい具体例の中でも、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,2,6-ヘキサントリオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールが好ましく、1,3-プロパンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,2,6-ヘキサントリオール、ペンタエリスリトールがより好ましく、ペンタエリスリトールが特に好ましい。本発明に係るアルコールは、市販のものでも、自体公知の方法によって適宜合成したものでもよい。 Among the preferred specific examples of the compounds represented by the general formulas (B3) to (B5), the alcohol according to the present invention includes 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol, dipentaerythritol are preferred, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1 2,6-hexanetriol and pentaerythritol are more preferred, and pentaerythritol is particularly preferred. The alcohol according to the present invention may be a commercially available one, or one appropriately synthesized by a method known per se.
［本発明の結着剤組成物］
　本発明の結着剤組成物は、（Ａ）ポリアクリル酸を含む１種以上のポリマー、（Ｂ）２価～１０価のアルコール、及び（Ｃ）水を含んでなるものである。尚、（Ｂ）２価～１０価のアルコールは、１種のみ用いても２種以上を組み合わせて用いてもよく、１種のみ用いるのが好ましい。 [Binder composition of the present invention]
The binder composition of the present invention comprises (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water. Note that (B) divalent to 10-valent alcohols may be used alone or in combination of two or more, and preferably only one is used.
　本発明の結着剤組成物における（Ａ）ポリアクリル酸を含む１種以上のポリマーの含有量は、本発明の結着剤組成物中の（Ａ）と（Ｂ）の総質量に対して７０～９９質量％、好ましくは７５～９９質量％、より好ましくは８０～９９質量％である。尚、（Ａ）が２種以上のポリマーである場合には、それらの総質量が上記含有量になればよい。 The content of one or more polymers including (A) polyacrylic acid in the binder composition of the present invention is based on the total mass of (A) and (B) in the binder composition of the present invention. It is 70 to 99% by mass, preferably 75 to 99% by mass, and more preferably 80 to 99% by mass. In addition, when (A) is 2 or more types of polymers, those total mass should just become said content.
　本発明の結着剤組成物における（Ｂ）２価～１０価のアルコールの含有量は、本発明の結着剤組成物中の（Ａ）と（Ｂ）の総質量に対して１～３０質量％、好ましくは１～２５質量％、より好ましくは１～２０質量％である。尚、（Ｂ）を２種以上組み合わせて用いる場合には、それらの総質量が上記含有量になればよい。 The content of the (B) divalent to 10-valent alcohol in the binder composition of the present invention is 1 to 30 relative to the total mass of (A) and (B) in the binder composition of the present invention. % By mass, preferably 1 to 25% by mass, more preferably 1 to 20% by mass. In addition, when using (B) combining 2 or more types, those total mass should just become said content.
　本発明の結着剤組成物における（Ｃ）水の含有量は、本発明の結着剤組成物中の（Ａ）と（Ｂ）の総質量が全体の１～５０質量％、好ましくは１～２０質量％となる量である。この時、本発明の結着剤組成物中の（Ａ）ポリアクリル酸を含む１種以上のポリマーの濃度は、電極調製に用いられる濃度に合わせて適宜設定されればよいが、通常１～３０％、好ましくは１～２０％である。 The content of (C) water in the binder composition of the present invention is such that the total mass of (A) and (B) in the binder composition of the present invention is 1 to 50% by mass, preferably 1 It is an amount that becomes ˜20 mass%. At this time, the concentration of the one or more polymers containing (A) polyacrylic acid in the binder composition of the present invention may be appropriately set according to the concentration used for electrode preparation. 30%, preferably 1 to 20%.
　本発明の結着剤組成物は、（Ａ）ポリアクリル酸を含む１種以上のポリマー、（Ｂ）２価～１０価のアルコール、及び（Ｃ）水を、それぞれ上記含有量となるように混合することにより製造し得る。このとき、（Ａ）ポリアクリル酸を含む１種以上のポリマーの製造方法における重合反応、中和処理及び架橋反応は、本発明の結着剤組成物を製造する前に予め行う必要がある。すなわち、上述した重合反応、並びに、要すれば中和処理及び／又は架橋反応を行い、所望の（Ａ）ポリアクリル酸を含む１種以上のポリマーを製造した上で、該ポリマーを（Ｂ）２価～１０価のアルコール及び（Ｃ）水と混合し、本発明の結着剤組成物を製造する必要がある。なぜなら、例えば上述した（Ａ）ポリアクリル酸を含む１種以上のポリマーの製造方法において、（Ｂ）２価～１０価のアルコールを加えて重合反応を行った場合、得られたポリマーが水を始めとする種々の溶媒に溶解しないという問題が生じ、該ポリマーを電極作製に用いることが出来ないためである。 The binder composition of the present invention is such that (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water have the above contents. It can be produced by mixing. At this time, (A) the polymerization reaction, neutralization treatment and crosslinking reaction in the method for producing one or more polymers containing polyacrylic acid need to be carried out in advance before producing the binder composition of the present invention. That is, after carrying out the above-described polymerization reaction and, if necessary, neutralization treatment and / or cross-linking reaction to produce one or more kinds of polymers containing the desired (A) polyacrylic acid, the polymer (B) It is necessary to produce the binder composition of the present invention by mixing with divalent to 10-valent alcohol and (C) water. This is because, for example, in the above-described method (A) for producing one or more polymers containing polyacrylic acid, when (B) a divalent to 10-valent alcohol is added and a polymerization reaction is performed, the resulting polymer contains water. This is because there is a problem that it does not dissolve in various solvents such as the beginning, and the polymer cannot be used for electrode preparation.
　本発明の結着剤組成物は、電極作製時に（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ｂ）２価～１０価のアルコールを介して結合することにより（該アルコールが連結剤として働くことにより）、該ポリマーが電極に均等に配置されて活物質表面を包み込むと考えられる。特に、（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ａ２）ポリアクリル酸と１種以上のポリアクリル酸以外のポリマーからなるポリマー群である場合、（Ｂ）２価～１０価のアルコールが異なるポリマー（例えば、ポリアクリル酸と本発明に係るコポリマー）間を結合することにより、電極作製時に相分離することを防ぐことが可能であると考えられる。そのため、本発明の結着剤組成物を用いて電極を作製すれば、活物質表面のほとんどを充放電に活用できるサイクル特性に優れた電極を得ることが出来る。 The binder composition of the present invention is produced by bonding (A) one or more polymers containing polyacrylic acid via (B) a divalent to 10-valent alcohol at the time of electrode preparation (the alcohol is a linking agent). It is believed that the polymer is evenly disposed on the electrode and envelops the active material surface. In particular, when (A) one or more polymers containing polyacrylic acid is a polymer group comprising (A2) polyacrylic acid and one or more polymers other than polyacrylic acid, It is considered that it is possible to prevent phase separation during electrode preparation by bonding between polymers having different alcohols (for example, polyacrylic acid and the copolymer according to the present invention). Therefore, if an electrode is produced using the binder composition of the present invention, an electrode having excellent cycle characteristics that can utilize most of the active material surface for charge and discharge can be obtained.
［シリコンを含有する活物質］
　本発明のスラリー組成物におけるシリコンを含有する活物質は、少なくともシリコンを含有するものであればよく、シリコンのみからなるものであっても、シリコンとシリコン以外の活物質材料からなるものであってもよい。 [Active material containing silicon]
The active material containing silicon in the slurry composition of the present invention is not limited as long as it contains at least silicon. Even if it is made of only silicon, it is made of active material other than silicon and silicon. Also good.
　上記シリコンとしては、シリコンの他に、ＳｉＯ、ＳｉＯ２等のシリコン酸化物、金属と結合したシリコン（ＳｉＭ：Ｍはマグネシウム、鉄、カルシウム、コバルト、ニッケル、ホウ素、銅、マンガン、銀、バナジウム、セリウム、亜鉛等の金属）等が挙げられ、シリコン、シリコン酸化物が好ましく、シリコンがより好ましい。 As the silicon, in addition to silicon, SiO, silicon oxides such as SiO 2, silicon bonded to a metal (SiM: M is magnesium, iron, calcium, cobalt, nickel, boron, copper, manganese, silver, vanadium, Metal such as cerium and zinc), and silicon and silicon oxide are preferable, and silicon is more preferable.
　また、上記シリコンは、その表面の一部又は全部に炭素を被覆したものであってもよい。具体的には例えば、表面に炭素を被覆したシリコン、表面に炭素を被覆したシリコン酸化物、表面に炭素を被覆した金属と結合したシリコン等が挙げられる。 In addition, the silicon may be one in which part or all of the surface is coated with carbon. Specifically, for example, silicon whose surface is coated with carbon, silicon oxide whose surface is coated with carbon, silicon bonded with a metal whose surface is coated with carbon, and the like can be given.
　上記シリコン以外の活物質材料としては、炭素、ゲルマニウム、錫、鉛、亜鉛、アルミニウム、インジウム、アンチモン、ビスマスなどが挙げられ、中でも炭素が好ましい。 Examples of the active material other than silicon include carbon, germanium, tin, lead, zinc, aluminum, indium, antimony, bismuth, and the like. Among these, carbon is preferable.
　上記炭素としては、例えば、天然黒鉛、人造黒鉛、膨張黒鉛等の黒鉛系炭素材料（黒鉛）、カーボンブラック、活性炭、カーボンファイバー、コークス、ソフトカーボン、ハードカーボン等が挙げられる。中でも天然黒鉛、人造黒鉛、膨張黒鉛等の黒鉛が好ましい。該天然黒鉛としては、鱗片状黒鉛、塊状黒鉛等が挙げられる。該人造黒鉛としては、塊状黒鉛、気相成長黒鉛、鱗片状黒鉛、繊維状黒鉛等が挙げられる。 Examples of the carbon include graphite-based carbon materials (graphite) such as natural graphite, artificial graphite, and expanded graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, and hard carbon. Of these, graphite such as natural graphite, artificial graphite, and expanded graphite is preferable. Examples of the natural graphite include flaky graphite and massive graphite. Examples of the artificial graphite include massive graphite, vapor-grown graphite, flaky graphite, and fibrous graphite.
　本発明のスラリー組成物におけるシリコンを含有する活物質としては、シリコン；シリコン酸化物；金属と結合したシリコン；これらから選ばれる２種以上を混合したもの；或いはこれらのうち少なくとも１種と、炭素、ゲルマニウム、錫、鉛、亜鉛、アルミニウム、インジウム、アンチモン、ビスマスから選ばれる１種以上を混合したものを含有する活物質が挙げられる。中でも、シリコン；シリコン酸化物；金属と結合したシリコン；これらから選ばれる２種以上を混合したもの；或いはこれらのうち少なくとも１種と、炭素及び／又は錫を混合したものを含有する活物質が好ましく、シリコン；シリコン酸化物；金属と結合したシリコン；或いは、炭素、シリコン、シリコン酸化物又は金属と結合したシリコンのうち少なくとも２種以上を混合したものを含有する活物質がより好ましく、シリコン；シリコン酸化物；或いは、炭素、シリコン又はシリコン酸化物のうち少なくとも２種以上を混合したものを含有する活物質がさらに好ましく、シリコン及び／又はシリコン酸化物を含有する活物質が特に好ましい。 Examples of the active material containing silicon in the slurry composition of the present invention include silicon, silicon oxide, silicon bonded to a metal, a mixture of two or more selected from these, or at least one of these and carbon. , An active material containing a mixture of at least one selected from germanium, tin, lead, zinc, aluminum, indium, antimony, and bismuth. Among them, an active material containing silicon; silicon oxide; silicon bonded to metal; a mixture of two or more selected from these; or a mixture of at least one of these and carbon and / or tin Preferably, silicon; silicon oxide; silicon bonded to metal; or an active material containing a mixture of carbon, silicon, silicon oxide or silicon bonded to metal is more preferable, and silicon; An active material containing silicon oxide; or a mixture of at least two of carbon, silicon, or silicon oxide is more preferred, and an active material containing silicon and / or silicon oxide is particularly preferred.
　本発明のスラリー組成物におけるシリコンを含有する活物質の平均粒子径は、活物質の種類により異なるが、通常１ｎｍ～１００μｍであり、好ましくは１ｎｍ～５０μｍであり、より好ましくは１ｎｍ～２０μｍである。 The average particle size of the active material containing silicon in the slurry composition of the present invention varies depending on the type of active material, but is usually 1 nm to 100 μm, preferably 1 nm to 50 μm, more preferably 1 nm to 20 μm. .
　本発明のスラリー組成物におけるシリコンを含有する活物質中のシリコンの含量は、通常１０～１００質量％であり、好ましくは４０～１００質量％であり、より好ましくは５０～１００質量％である。 The silicon content in the active material containing silicon in the slurry composition of the present invention is usually 10 to 100% by mass, preferably 40 to 100% by mass, and more preferably 50 to 100% by mass.
［導電助剤］
　本発明のスラリー組成物における導電助剤は、例えば、アセチレンブラック、ケッチェンブラック、ファーネスブラック、サーマルブラック等のカーボンブラックが挙げられ、中でもアセチレンブラック、ケッチェンブラックが好ましく、アセチレンブラックがより好ましい。 [Conductive aid]
Examples of the conductive auxiliary in the slurry composition of the present invention include carbon blacks such as acetylene black, ketjen black, furnace black, and thermal black. Among them, acetylene black and ketjen black are preferable, and acetylene black is more preferable.
［本発明のスラリー組成物］
　本発明のスラリー組成物は、１）シリコンを含有する活物質、２）導電助剤、及び３）本発明の結着剤組成物を含んでなる、電極作製用の組成物である。本発明のスラリー組成物は、陽極作製用であっても負極作製用であってもよいが、負極作製用として用いられるのが好ましい。 [Slurry composition of the present invention]
The slurry composition of the present invention is a composition for producing an electrode comprising 1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a binder composition of the present invention. The slurry composition of the present invention may be used for preparing an anode or a negative electrode, but is preferably used for preparing a negative electrode.
　本発明のスラリー組成物におけるシリコンを含有する活物質の含有量は、溶媒を含まないスラリー組成物の質量に対して１～９８質量％、好ましくは１０～９８質量％である。 The content of the active material containing silicon in the slurry composition of the present invention is 1 to 98% by mass, preferably 10 to 98% by mass, based on the mass of the slurry composition not containing the solvent.
　本発明のスラリー組成物における導電助剤の含有量は、溶媒を含まないスラリー組成物の質量に対して１～４０質量％、好ましくは１～３０質量％、より好ましくは１～２０質量％である。 The content of the conductive assistant in the slurry composition of the present invention is 1 to 40% by mass, preferably 1 to 30% by mass, more preferably 1 to 20% by mass with respect to the mass of the slurry composition not containing the solvent. is there.
　本発明のスラリー組成物における本発明の結着剤組成物の含有量は、溶媒を含まないスラリー組成物の質量に対して１～３０質量％、より好ましくは１～２５質量％、さらに好ましくは１～２０質量％である。この範囲で本発明の結着剤組成物を含有させることにより、電極作製時に活物質及び導電助剤を集電体上に均一に分散させ、且つ、シリコン膨張時であっても電極構造を維持することができる。 The content of the binder composition of the present invention in the slurry composition of the present invention is 1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably based on the mass of the slurry composition not containing a solvent. 1 to 20% by mass. By including the binder composition of the present invention within this range, the active material and the conductive assistant are uniformly dispersed on the current collector during electrode production, and the electrode structure is maintained even during silicon expansion. can do.
　本発明のスラリー組成物は、１）シリコンを含有する活物質、２）導電助剤、及び３）本発明の結着剤組成物以外に、例えば、支持塩、イオン伝導性ポリマー、バインダーポリマー等を含んでいてもよい（ただし、本発明の結着剤組成物における（Ａ）ポリアクリル酸を含む１種以上のポリマーに含まれるものを除く）。該支持塩としては、例えばLi(C2F5SO2)2N（LiBETI）、LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3等が挙げられる。該イオン伝導性ポリマーとしては、例えばポリエチレンオキシド（PEO）系のポリマー、ポリプロピレンオキシド（PPO）系のポリマー等が挙げられる。該バインダーポリマーとしては、例えばポリフッ化ビニリデン（PVDF）、ポリテトラフルオロエチレン（PTFE）、カルボキシメチルセルロース（CMC）、スチレンブタジエン共重合体（SBR）、アクリロニトリルブタジエン共重合体（NBR）、ポリアクリロニトリル（PAN）、エチレンビニルアルコール共重合体（EVOH)、ポリウレタン、ポリアクリレート、ポリビニルエーテル、ポリイミド等が挙げられる。これら支持塩、イオン伝導性ポリマー及びバインダーポリマーの含有量は、通常この分野で用いられる量に準じて設定されればよい。 The slurry composition of the present invention includes 1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a binder composition of the present invention, for example, a supporting salt, an ion conductive polymer, a binder polymer, and the like. (However, (A) in the binder composition of the present invention, excluding those contained in one or more polymers containing polyacrylic acid). Examples of the supporting salt include Li (C 2 F 5 SO 2 ) 2 N (LiBETI), LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like. Examples of the ion conductive polymer include polyethylene oxide (PEO) -based polymers and polypropylene oxide (PPO) -based polymers. Examples of the binder polymer include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), styrene butadiene copolymer (SBR), acrylonitrile butadiene copolymer (NBR), and polyacrylonitrile (PAN). ), Ethylene vinyl alcohol copolymer (EVOH), polyurethane, polyacrylate, polyvinyl ether, polyimide and the like. The contents of the supporting salt, the ion conductive polymer and the binder polymer may be set according to the amounts usually used in this field.
　本発明のスラリー組成物は、１）シリコンを含有する活物質、２）導電助剤、及び３）本発明の結着剤組成物を適当な溶媒中でそれぞれ上記濃度範囲となるように混合することにより得られる。該溶媒としては、例えば、水、N-メチル-2-ピロリドン（NMP）、ジメチルホルムアミド、ジメチルアセトアミド、メチルホルムアミド、ジメチルスルホキシド、アセトニトリル、テトラヒドロフラン、γ-ブチロラクトン、トルエン、メチルエチルケトン、酢酸エチル、ジオキサン等が挙げられ、水が好ましい。 In the slurry composition of the present invention, 1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a binder composition of the present invention are mixed in an appropriate solvent so as to be within the above-mentioned concentration range. Can be obtained. Examples of the solvent include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, γ-butyrolactone, toluene, methyl ethyl ketone, ethyl acetate, dioxane and the like. And water is preferred.
［集電体］
　本発明に係る集電体は、ニッケル、銅、ステンレス（SUS）などの導電性の材料を用いた箔、メッシュ、エキスパンドグリッド（エキスパンドメタル）、パンチドメタル等から構成される。メッシュの目開き、線径、メッシュ数等は特に制限されず、従来公知のものが使用できる。集電体の好ましい厚さは、５～３０μｍである。ただし、この範囲を外れる厚さの集電体を用いてもよい。 [Current collector]
The current collector according to the present invention includes a foil, a mesh, an expanded grid (expanded metal), a punched metal, and the like using a conductive material such as nickel, copper, and stainless steel (SUS). The mesh opening, wire diameter, number of meshes and the like are not particularly limited, and conventionally known ones can be used. The preferred thickness of the current collector is 5 to 30 μm. However, a current collector having a thickness outside this range may be used.
　集電体の大きさは、電池の使用用途に応じて決定される。大型の電池に用いられる大型の電極を作製するのであれば、面積の大きな集電体が用いられる。小型の電極を作製するのであれば、面積の小さな集電体が用いられる。 The size of the current collector is determined according to the intended use of the battery. If a large electrode used for a large battery is manufactured, a current collector having a large area is used. If a small electrode is produced, a current collector with a small area is used.
［本発明の電極］
　本発明の電極は、１）シリコンを含有する活物質、２）導電助剤、３）本発明の結着剤組成物由来の結着剤、及び４）集電体を有するものである。具体的には、集電体と、その表面に形成された、シリコンを含有する活物質、導電助剤及び本発明の結着剤組成物由来の結着剤を含む活物質層とを有するものである。本発明の電極は、負極としても陽極としても用いることができるが、負極として用いるのが好ましい。 [Electrode of the present invention]
The electrode of the present invention has 1) an active material containing silicon, 2) a conductive additive, 3) a binder derived from the binder composition of the present invention, and 4) a current collector. Specifically, it has a current collector and an active material layer formed on the surface thereof, including an active material containing silicon, a conductive additive, and a binder derived from the binder composition of the present invention. It is. The electrode of the present invention can be used as a negative electrode or an anode, but is preferably used as a negative electrode.
　上記活物質層においては、本発明の結着剤組成物由来の結着剤が、シリコンを含有する活物質と導電助剤とを集電体上に均一に分散し、且つ、良好な被覆性を保つため、本発明の電極は可逆性に優れる。 In the active material layer, the binder derived from the binder composition of the present invention uniformly disperses the active material containing silicon and the conductive additive on the current collector, and has good coverage. Therefore, the electrode of the present invention is excellent in reversibility.
　上記活物質層の厚さ（塗布層の厚さ）は、通常１～５００μｍであり、好ましくは１～３００μｍであり、より好ましくは１～１５０μｍである。 The thickness of the active material layer (the thickness of the coating layer) is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 1 to 150 μm.
　本発明の電極の作製方法は、本発明のスラリー組成物〔１）シリコンを含有する活物質、２）導電助剤及び３）本発明の結着剤組成物を含む組成物〕を集電体上に塗布し、乾燥させることを特徴とする。該作製方法において本発明のスラリー組成物を乾燥させることにより、本発明の結着剤組成物中の（Ａ）ポリアクリル酸を含む１種以上のポリマーが（Ｂ）２～１０価のアルコールを介して結合し、本発明の結着剤組成物由来の結着剤を形成する。
　該作製方法において、本発明のスラリー組成物の使用量は、乾燥後に活物質層の厚さが上記範囲になるよう適宜設定すればよい。 A method for producing an electrode of the present invention comprises a slurry composition [1) an active material containing silicon, 2) a conductive auxiliary agent, and 3) a composition containing the binder composition of the present invention] as a current collector. It is characterized by being coated on top and dried. In the preparation method, the slurry composition of the present invention is dried, so that (A) one or more kinds of polymers including polyacrylic acid in the binder composition of the present invention are converted into (B) a divalent to 10-valent alcohol. To form a binder derived from the binder composition of the present invention.
In the production method, the amount of the slurry composition of the present invention used may be appropriately set so that the thickness of the active material layer is within the above range after drying.
　本発明の電極の作製方法における本発明のスラリー組成物を集電体に塗布する方法としては、例えば、自走型コータ、インクジェット法、ドクターブレード法、スプレー法、またはこれらの組み合わせを用いることができる。中でも、薄い層を形成できるドクターブレード法やインクジェット法が好ましく、ドクターブレード法がより好ましい。 As a method for applying the slurry composition of the present invention to the current collector in the method for producing an electrode of the present invention, for example, a self-propelled coater, an ink jet method, a doctor blade method, a spray method, or a combination thereof may be used. it can. Among these, a doctor blade method and an ink jet method capable of forming a thin layer are preferable, and a doctor blade method is more preferable.
　本発明の電極の作製方法における乾燥方法としては、自体公知の方法に準じてなされればよく、通常加熱処理によりなされる。加熱時の乾燥条件（真空の要否、乾燥時間、乾燥温度）は、本発明のスラリー組成物の塗布量や揮発速度に応じて適宜設定されればよい。具体的には例えば、真空中、通常８０～１５０℃、好ましくは１２０～１５０℃で、通常５～２０時間、好ましくは６～１２時間乾燥させればよい。 The drying method in the method for producing an electrode of the present invention may be performed according to a method known per se, and is usually performed by heat treatment. The drying conditions during heating (necessity of vacuum, drying time, drying temperature) may be appropriately set according to the coating amount and volatilization rate of the slurry composition of the present invention. Specifically, for example, it may be dried at 80 to 150 ° C., preferably 120 to 150 ° C. in a vacuum, usually for 5 to 20 hours, preferably 6 to 12 hours.
　本発明の電極の作製方法において、要すれば乾燥後にプレス処理を行ってもよい。該プレス方法としては、自体公知の方法に準じてなされればよく、例えばカレンダーロール法、平板プレス等が挙げられ、カレンダーロール法が好ましい。 In the electrode manufacturing method of the present invention, if necessary, press treatment may be performed after drying. The pressing method may be performed according to a method known per se, and examples thereof include a calender roll method and a flat plate press, and the calender roll method is preferable.
　本発明の電極は、リチウム電池に用いることができるものであり、正極、電解質、負極で構成される通常の電池であれば何れにも用いることができる。 The electrode of the present invention can be used for a lithium battery, and can be used for any ordinary battery including a positive electrode, an electrolyte, and a negative electrode.
　該電解質としては、ビニレンカーボネート、フルオロビニレンカーボネート、メチルビニレンカーボネート、フルオロメチルビニレンカーボネート、エチルビニレンカーボネート、プロピルビニレンカーボネート、ブチルビニレンカーボンネード、ジプロピルビニレンカーボネート、4,5-ジメチルビニレンカーボネート、4,5-ジエチルビニレンカーボネート、ビニルエチレンカーボネート、ジビニルエチレンカーボネート、フェニルエチレンカーボネート、ジアリルカーボネート、フルオロエチレンカーボネート（FEC）、カテコールカーボネート、1,3-プロパンスルトン及びブタンスルトン等の添加剤を有するものが好ましく、中でもフルオロエチレンカーボネート（FEC）を有するものがより好ましい。電解質中の添加剤の含有量は、通常０．５％～１５％であり、０．５～５％が好ましい。 Examples of the electrolyte include vinylene carbonate, fluorovinylene carbonate, methyl vinylene carbonate, fluoromethyl vinylene carbonate, ethyl vinylene carbonate, propyl vinylene carbonate, butyl vinylene carbonate, dipropyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5 -Those having additives such as diethyl vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, phenyl ethylene carbonate, diallyl carbonate, fluoroethylene carbonate (FEC), catechol carbonate, 1,3-propane sultone and butane sultone are preferred. Those having ethylene carbonate (FEC) are more preferred. The content of the additive in the electrolyte is usually 0.5% to 15%, preferably 0.5 to 5%.
　以下、実施例により本発明を詳細に説明するが、本発明はこれにより限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
合成例１　架橋コポリマーＣ－１の合成
　攪拌装置、冷却管、温度計、窒素導入管及び滴下装置を備えた200mLの丸底フラスコに、プロピレングリコールモノメチルエーテルアセテート70g（530mmol、和光純薬工業(株)製）を入れ、窒素気流下で内温が９０℃になるまで加熱した。次いで、アクリル酸9.2g（128mmol、和光純薬工業(株)製）、アクリル酸-2-ヒドロキシエチル（ＨＥＡ）9.2g（79mmol、和光純薬工業(株)製）、ポリエチレングリコールジアクリレート0.06g（0.2mmol、新中村化学工業(株)製）、2,2’-アゾビス(イソブチルニトリル)0.04g（0.2mmol、和光純薬工業(株)製）及びプロピレングリコールモノメチルエーテルアセテート30g（227mmol）を混合した溶液を、２時間かけて丸底フラスコに滴下した。その後、得られた溶液を９０℃で５時間反応させた。反応後、室温まで冷却し、架橋されたコポリマーを得た。25mmHg（約33.3hPa）減圧下で得られたコポリマーからプロピレングリコールモノメチルエーテルアセテートを除去して固形状物を得た後、さらに真空乾燥して、モノマー組成比がアクリル酸：ＨＥＡ＝１：１の固形分を得た。これを架橋コポリマーＣ－１とした。 Synthesis Example 1 Synthesis of crosslinked copolymer C-1 In a 200 mL round bottom flask equipped with a stirring device, a cooling tube, a thermometer, a nitrogen introduction tube and a dropping device, 70 g of propylene glycol monomethyl ether acetate (530 mmol, Wako Pure Chemical Industries, Ltd. )) And heated under a nitrogen stream until the internal temperature reached 90 ° C. Next, 9.2 g of acrylic acid (128 mmol, manufactured by Wako Pure Chemical Industries, Ltd.), 9.2 g of 2-hydroxyethyl acrylate (HEA) (79 mmol, manufactured by Wako Pure Chemical Industries, Ltd.), 0.06 g of polyethylene glycol diacrylate (0.2 mmol, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2′-azobis (isobutylnitrile) 0.04 g (0.2 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) and 30 g (227 mmol) of propylene glycol monomethyl ether acetate The mixed solution was added dropwise to the round bottom flask over 2 hours. Thereafter, the obtained solution was reacted at 90 ° C. for 5 hours. After the reaction, it was cooled to room temperature to obtain a crosslinked copolymer. After removing propylene glycol monomethyl ether acetate from the copolymer obtained under reduced pressure at 25 mmHg (about 33.3 hPa) to obtain a solid product, it was further dried under vacuum to have a monomer composition ratio of acrylic acid: HEA = 1: 1. A solid was obtained. This was designated as a crosslinked copolymer C-1.
合成例２　非架橋コポリマーＣ－２の合成
　ポリエチレングリコールジアクリレートを添加しない以外は合成例１と同様の方法で重合反応に付し、非架橋コポリマーＣ－２を得た。 Synthesis Example 2 Synthesis of Non-Crosslinked Copolymer C-2 A non-crosslinked copolymer C-2 was obtained by subjecting it to a polymerization reaction in the same manner as in Synthesis Example 1 except that polyethylene glycol diacrylate was not added.
合成例３　架橋ホモポリマーＡ－１の合成
　アクリル酸-2-ヒドロキシエチルを添加せず、アクリル酸を9.2g（128mmol）の代わりに18.4g（255mmol）用いた以外は、合成例１と同様の方法で重合反応に付し、架橋ホモポリマーＡ－１を得た。 Synthesis Example 3 Synthesis of crosslinked homopolymer A-1 The same as Synthesis Example 1 except that 18.4 g (255 mmol) of acrylic acid was used instead of 9.2 g (128 mmol) without adding 2-hydroxyethyl acrylate. The polymer was subjected to a polymerization reaction to obtain a crosslinked homopolymer A-1.
合成例４　架橋ホモポリマーＡ－２の合成
　アクリル酸-2-ヒドロキシエチルを添加せず、アクリル酸を9.2g（128mmol）の代わりに18.4g（255mmol）、2,2’-アゾビス(イソブチルニトリル)を0.04g（0.2mmol）の代わりに0.2g（1mmol）用いた以外は、合成例１と同様の方法で重合反応に付し、架橋ホモポリマーＡ－２を得た。 Synthesis Example 4 Synthesis of Crosslinked Homopolymer A-2 Acrylic acid instead of 9.2 g (128 mmol) was added with 18.4 g (255 mmol) of 2,2′-azobis (isobutylnitrile) without adding 2-hydroxyethyl acrylate Was subjected to a polymerization reaction in the same manner as in Synthesis Example 1 except that 0.2 g (1 mmol) was used instead of 0.04 g (0.2 mmol) to obtain a crosslinked homopolymer A-2.
合成例５　架橋コポリマー溶液Ｈ－５の調製
　100mLのガラス製ビーカーに架橋コポリマーＣ－１を4.6g、イオン交換水30mLを加え、２時間撹拌して分散させた。得られた分散液に５０％水酸化ナトリウム溶液（和光純薬工業(株)製）を加えてｐＨを６．８に調整した後、イオン交換水で全量が50gになるように調整し、固形分が１０ｗｔ％の中和した架橋コポリマーの溶液50gを得た（中和度８０％）。これを、架橋コポリマー溶液Ｈ－５とした。 Synthesis Example 5 Preparation of crosslinked copolymer solution H-5 To a 100 mL glass beaker, 4.6 g of crosslinked copolymer C-1 and 30 mL of ion-exchanged water were added and dispersed by stirring for 2 hours. A 50% sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to the resulting dispersion to adjust the pH to 6.8, and the total amount is adjusted to 50 g with ion-exchanged water. 50 g of a neutralized crosslinked copolymer solution having a content of 10 wt% was obtained (degree of neutralization 80%). This was designated as a crosslinked copolymer solution H-5.
合成例６　非架橋コポリマー溶液Ｈ－６の調製
　架橋コポリマーＣ－１　4.6gの代わりに非架橋コポリマーＣ－２　4.6gを用いた以外は、合成例５と同様の方法により、中和した非架橋コポリマーの溶液を得た（中和度８０％）。これを、非架橋コポリマー溶液Ｈ－６とした。 Synthesis Example 6 Preparation of Non-crosslinked Copolymer Solution H-6 Neutralized non-crosslinked by the same method as Synthesis Example 5 except that 4.6 g of non-crosslinked copolymer C-2 was used instead of 4.6 g of crosslinked copolymer C-1 A solution of copolymer was obtained (degree of neutralization 80%). This was designated as non-crosslinked copolymer solution H-6.
合成例７　架橋ホモポリマー溶液Ｈ－２の調製
　100mLのガラス製ビーカーに架橋ホモポリマーＡ－１を3.8g、イオン交換水20mLを加え、２時間撹拌して分散させた。得られた分散液に５０％水酸化ナトリウム溶液（和光純薬工業(株)製）を加えてｐＨを６．８に調整した後、イオン交換水で全量が50gになるように調整し、固形分が１０ｗｔ％の中和した架橋ホモポリマーの溶液50gを得た（中和度８０％）。これを、架橋ホモポリマー溶液Ｈ－２とした。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により架橋ホモポリマー溶液Ｈ－２の重量平均分子量（Mw）を求めたところ、1,100,000であった。
　ＧＰＣによる測定は下記条件で行った。
・測定装置：ポンプ　LC-20AB（(株)島津製作所製）
　　　　　　ＲＩ検出器　RID-10A（(株)島津製作所製）
・カラム：OHpak　SB-807　HQ×１本
　　　　　＋OHpak　SB-806M　HQ×２本
・移動相：Ｎａ２ＨＰＯ４　50mmol/l水溶液
・検量線標準物質：ポリアクリル酸 Synthesis Example 7 Preparation of crosslinked homopolymer solution H-2 3.8 g of crosslinked homopolymer A-1 and 20 mL of ion-exchanged water were added to a 100 mL glass beaker and dispersed by stirring for 2 hours. A 50% sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to the resulting dispersion to adjust the pH to 6.8, and the total amount is adjusted to 50 g with ion-exchanged water. 50 g of a neutralized crosslinked homopolymer solution having a content of 10 wt% was obtained (degree of neutralization 80%). This was designated as a crosslinked homopolymer solution H-2. When the weight average molecular weight (Mw) of the crosslinked homopolymer solution H-2 was determined by gel permeation chromatography (GPC), it was 1,100,000.
The measurement by GPC was performed under the following conditions.
・ Measurement device: Pump LC-20AB (manufactured by Shimadzu Corporation)
RI detector RID-10A (manufactured by Shimadzu Corporation)
Column: OHpak SB-807 HQ × 1 present + OHpak SB-806M HQ × 2 present Mobile phase: Na 2 HPO 4 50mmol / l aqueous solution, a calibration curve standard: polyacrylic acid
合成例８　架橋ホモポリマー溶液Ｈ－１の調整
　架橋ホモポリマーＡ－１　3.8gの代わりに架橋ホモポリマーＡ－２　3.8gを用いた以外は、合成例７と同様の方法により、中和した架橋ホモポリマーの溶液を得た（中和度８０％）。これを、架橋ホモポリマー溶液Ｈ－１とした。ＧＰＣにより架橋ホモポリマー溶液Ｈ－１の重量平均分子量（Mw）を求めたところ、300,000であった。 Synthesis Example 8 Preparation of Cross-linked Homopolymer Solution H-1 Neutralized cross-linking by the same method as in Synthetic Example 7 except that 3.8 g of cross-linked homopolymer A-2 was used instead of 3.8 g of cross-linked homopolymer A-1. A homopolymer solution was obtained (degree of neutralization 80%). This was designated as a crosslinked homopolymer solution H-1. When the weight average molecular weight (Mw) of the crosslinked homopolymer solution H-1 was determined by GPC, it was 300,000.
合成例９　非架橋ホモポリマー溶液Ｈ－３の調整
　100mLのガラス製ビーカーに重量平均分子量250,000のポリアクリル酸3.8g（和光純薬工業(株)製）とイオン交換水20mLを加え、２時間撹拌して分散させた。得られた分散液に５０％水酸化ナトリウム溶液（和光純薬工業(株)製）を加えてｐＨを６．８に調整した後、イオン交換水で全量が50gになるように調整し、固形分が１０ｗｔ％の中和した非架橋ホモポリマーの溶液50gを得た（中和度８０％）。これを、非架橋ホモポリマー溶液Ｈ－３とした。 Synthesis Example 9 Preparation of non-crosslinked homopolymer solution H-3 In a 100 mL glass beaker, 3.8 g of polyacrylic acid having a weight average molecular weight of 250,000 (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 mL of ion-exchanged water were added and stirred for 2 hours. And dispersed. A 50% sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to the resulting dispersion to adjust the pH to 6.8, and the total amount is adjusted to 50 g with ion-exchanged water. 50 g of a neutralized non-crosslinked homopolymer solution having a content of 10 wt% was obtained (degree of neutralization 80%). This was designated as non-crosslinked homopolymer solution H-3.
合成例１０　非架橋ホモポリマー溶液Ｈ－４の調整
　重量平均分子量250,000のポリアクリル酸3.8gの代わりに重量平均分子量1,000,000のポリアクリル酸3.8g（和光純薬工業(株)製）を用いた以外は、合成例９と同様の方法により、中和した非架橋ホモポリマーの溶液を得た（中和度８０％）。これを、非架橋ホモポリマー溶液Ｈ－４とした。 Synthesis Example 10 Preparation of non-crosslinked homopolymer solution H-4 Except for using 3.8 g of polyacrylic acid having a weight average molecular weight of 1,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.) instead of 3.8 g of polyacrylic acid having a weight average molecular weight of 250,000 Obtained a neutralized non-crosslinked homopolymer solution by the same method as in Synthesis Example 9 (degree of neutralization 80%). This was designated as non-crosslinked homopolymer solution H-4.
実験例１　各種ポリマー溶液の粘度測定
　合成例５～１０で得られた各種ポリマー溶液（架橋ホモポリマー溶液Ｈ－１及びＨ－２、非架橋ホモポリマー溶液Ｈ－３及びＨ－４、架橋コポリマー溶液Ｈ－５、並びに非架橋コポリマー溶液Ｈ－６）の粘度を、Ｂ型回転粘度計（商品名：B8L、株式会社東京計器製）でローターNo.4を使用して、回転速度12rpm、測定温度２０℃で測定した。
　得られた結果を重量平均分子量及び中和度と合わせて表１に示す。 Experimental Example 1 Viscosity measurement of various polymer solutions Various polymer solutions obtained in Synthesis Examples 5 to 10 (crosslinked homopolymer solutions H-1 and H-2, non-crosslinked homopolymer solutions H-3 and H-4, crosslinked copolymer solution) The viscosity of H-5 and non-crosslinked copolymer solution H-6) was measured with a B-type rotational viscometer (trade name: B8L, manufactured by Tokyo Keiki Co., Ltd.) using rotor No. 4, rotation speed 12 rpm, measurement temperature Measured at 20 ° C.
The obtained results are shown in Table 1 together with the weight average molecular weight and the degree of neutralization.
Figure JPOXMLDOC01-appb-T000147
Figure JPOXMLDOC01-appb-T000147
合成例１１　バインダー溶液Ｋ－１の調整
　テフロン（登録商標）製10mLのビーカーに架橋ホモポリマー溶液Ｈ－２　8.9g（固形分として0.89g）、架橋コポリマー溶液Ｈ－５　1g（固形分として0.1g）、ペンタエリスリトール0.01g（和光純薬工業(株)製）及びイオン交換水９０μＬを加えて、透明な溶液になるまで撹拌し、固形分が１０ｗｔ％のバインダー溶液Ｋ－１を得た。 Synthesis Example 11 Preparation of binder solution K-1 In a 10 mL beaker made of Teflon (registered trademark), 8.9 g of a crosslinked homopolymer solution H-2 (0.89 g as a solid content) and 1 g of a crosslinked copolymer solution H-5 (0.1 g as a solid content) ), 0.01 g of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) and 90 μL of ion-exchanged water were added and stirred until a transparent solution was obtained to obtain a binder solution K-1 having a solid content of 10 wt%.
合成例１２　バインダー溶液Ｋ－２の調整
　テフロン（登録商標）製10mLのビーカーに架橋ホモポリマー溶液Ｈ－２　8g（固形分として0.8g）、架橋コポリマー溶液Ｈ－５　1g（固形分として0.1g）、ペンタエリスリトール0.1g及びイオン交換水９００μＬを加えて、透明な溶液になるまで撹拌し、固形分が１０ｗｔ％のバインダー溶液Ｋ－２を得た。 Synthesis Example 12 Preparation of Binder Solution K-2 In a 10 mL beaker made of Teflon (registered trademark), 8 g of crosslinked homopolymer solution H-2 (0.8 g as solid content) and 1 g of crosslinked copolymer solution H-5 (0.1 g as solid content) Then, 0.1 g of pentaerythritol and 900 μL of ion-exchanged water were added and stirred until a transparent solution was obtained, thereby obtaining a binder solution K-2 having a solid content of 10 wt%.
合成例１３～１６　バインダー溶液Ｋ－３～６の調整
　ペンタエリスリトール0.1gの代わりに、1,3-プロパンジオール（和光純薬工業(株)製）、1,4-ブタンジオール（和光純薬工業(株)製）、1,6-ヘキサンジオール（和光純薬工業(株)製）又は1,2,6-ヘキサントリオール（和光純薬工業(株)製）をそれぞれ0.1g用いた以外は合成例１２と同様の方法により、固形分が１０ｗｔ％のバインダー溶液Ｋ－３～６を得た。 Synthesis Examples 13 to 16 Preparation of binder solution K-3 to 6 Instead of 0.1 g of pentaerythritol, 1,3-propanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 1,4-butanediol (Wako Pure Chemical Industries, Ltd.) Co., Ltd.), 1,6-hexanediol (Wako Pure Chemical Industries, Ltd.) or 1,2,6-hexanetriol (Wako Pure Chemical Industries, Ltd.) was used except for 0.1 g each. In the same manner as in Example 12, binder solutions K-3 to 6 having a solid content of 10 wt% were obtained.
合成例１７　バインダー溶液Ｋ－７の調整
　テフロン（登録商標）製10mLのビーカーに架橋ホモポリマー溶液Ｈ－２　7g（固形分として0.7g）、架橋コポリマー溶液Ｈ－５　1g（固形分として0.1g）、1,4-ブタンジオール0.2g及びイオン交換水１８００μＬを加えて、透明な溶液になるまで撹拌し、固形分が１０ｗｔ％のバインダー溶液Ｋ－７を得た。 Synthesis Example 17 Preparation of binder solution K-7 In a 10 mL beaker made of Teflon (registered trademark), 7 g of crosslinked homopolymer solution H-2 (0.7 g as solid content), 1 g of crosslinked copolymer solution H-5 (0.1 g as solid content) Then, 0.2 g of 1,4-butanediol and 1800 μL of ion-exchanged water were added and stirred until a transparent solution was obtained to obtain a binder solution K-7 having a solid content of 10 wt%.
合成例１８　バインダー溶液Ｋ－８の調整
　テフロン（登録商標）製10mLのビーカーに架橋ホモポリマー溶液Ｈ－２　9g（固形分として0.9g）、1,3-プロパンジオール0.1g及びイオン交換水１８００μＬを加えて、透明な溶液になるまで撹拌し、固形分が１０ｗｔ％のバインダー溶液Ｋ－８を得た。 Synthesis Example 18 Preparation of binder solution K-8 In a 10 mL beaker made of Teflon (registered trademark), 9 g of a crosslinked homopolymer solution H-2 (0.9 g as a solid content), 0.1 g of 1,3-propanediol and 1800 μL of ion-exchanged water were added. In addition, the mixture was stirred until a transparent solution was obtained, thereby obtaining a binder solution K-8 having a solid content of 10 wt%.
合成例１９　バインダー溶液Ｋ－９の調整
　架橋ホモポリマー溶液Ｈ－２　8gの代わりに非架橋ホモポリマー溶液Ｈ－３　8g（固形分として0.8g）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｋ－９を得た。 Synthesis Example 19 Method similar to Synthesis Example 12 except that 8 g of non-crosslinked homopolymer solution H-3 (0.8 g as solid content) was used instead of 8 g of the adjusted crosslinked homopolymer solution H-2 of binder solution K-9 As a result, a binder solution K-9 having a solid content of 10 wt% was obtained.
合成例２０　バインダー溶液Ｋ－１０の調整
　架橋ホモポリマー溶液Ｈ－２　8gの代わりに架橋ホモポリマー溶液Ｈ－１　8g（固形分として0.8g）を、架橋コポリマー溶液Ｈ－５　1gの代わりに非架橋コポリマー溶液Ｈ－６　1g（固形分として0.1g）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｋ－１０を得た。 Synthesis Example 20 Preparation of Binder Solution K-10 Crosslinked homopolymer solution H-2 (8 g) instead of crosslinked homopolymer solution H-2 (8 g) (solid content: 0.8 g) and crosslinked copolymer solution H-5 (1 g) were not crosslinked. A binder solution K-10 having a solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12 except that 1 g of the copolymer solution H-6 (0.1 g as the solid content) was used.
合成例２１　バインダー溶液Ｋ－１１の調整
　架橋ホモポリマー溶液Ｈ－２　8gの代わりに非架橋ホモポリマー溶液Ｈ－３　8g（固形分として0.8g）を、架橋コポリマー溶液Ｈ－５　1gの代わりに非架橋コポリマー溶液Ｈ－６　1g（固形分として0.1g）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｋ－１１を得た。 Synthesis Example 21 Preparation of Binder Solution K-11 Non-crosslinked homopolymer solution H-3 8 g (0.8 g as a solid content) instead of cross-linked homopolymer solution H-2 8 g A binder solution K-11 having a solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12, except that 1 g of the crosslinked copolymer solution H-6 (0.1 g as the solid content) was used.
合成例２２　バインダー溶液Ｋ－１２の調整
　架橋ホモポリマー溶液Ｈ－２　8gの代わりに非架橋ホモポリマー溶液Ｈ－４　8g（固形分として0.8g）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｋ－１２を得た。 Synthesis Example 22 Method similar to Synthesis Example 12 except that 8 g of non-crosslinked homopolymer solution H-4 (0.8 g as solid content) was used instead of 8 g of the adjusted crosslinked homopolymer solution H-2 of binder solution K-12 As a result, a binder solution K-12 having a solid content of 10 wt% was obtained.
合成例２３　バインダー溶液Ｋ－１３の調整
　架橋コポリマー溶液Ｈ－５　1gの代わりに非架橋コポリマー溶液Ｈ－６　1g（固形分として0.1g）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｋ－１３を得た。 Synthesis Example 23 Preparation of Binder Solution K-13 A solid solid was prepared in the same manner as in Synthesis Example 12 except that 1 g of non-crosslinked copolymer solution H-6 (0.1 g as the solid content) was used instead of 1 g of crosslinked copolymer solution H-5. A binder solution K-13 having a content of 10 wt% was obtained.
合成例２４　バインダー溶液Ｋ－１４の調整
　架橋ホモポリマー溶液Ｈ－２　8gの代わりに非架橋ホモポリマー溶液Ｈ－４　8g（固形分として0.8g）を、架橋コポリマー溶液Ｈ－５　1gの代わりに非架橋コポリマー溶液Ｈ－６　1g（固形分として0.1g）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｋ－１４を得た。 Synthesis Example 24 Preparation of Binder Solution K-14 Non-crosslinked homopolymer solution H-4 8 g (0.8 g as a solid content) instead of 8 g of crosslinked cross-linked homopolymer solution H-2 A binder solution K-14 having a solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12 except that 1 g of the crosslinked copolymer solution H-6 (0.1 g as the solid content) was used.
合成例２５　バインダー溶液Ｊ－１の調整
　ペンタエリスリトール0.1gの代わりにプロパンジアミン0.1g（和光純薬工業(株)製）を用いた以外は、合成例１２と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｊ－１を得た。 Synthesis Example 25 Preparation of Binder Solution J-1 A solid content of 10 wt% was obtained in the same manner as in Synthesis Example 12 except that 0.1 g of propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.1 g of pentaerythritol. Binder solution J-1 was obtained.
合成例２４　バインダー溶液Ｊ－２の調整
　ペンタエリスリトール0.01gの代わりにシュウ酸ナトリウム0.01g（和光純薬工業(株)製）を用いた以外は、合成例１１と同様の方法により固形分が１０ｗｔ％のバインダー溶液Ｊ－２を得た。 Synthesis Example 24 Preparation of Binder Solution J-2 A solid content of 10 wt.% Was obtained in the same manner as in Synthesis Example 11 except that 0.01 g of sodium oxalate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.01 g of pentaerythritol. % Binder solution J-2 was obtained.
実施例１　本発明の電極を用いた電池の製造
（１）本発明のスラリー組成物の製造
　シリコン粉末8g（粒子サイズ：平均粒径２．４μｍ、商品名：Silgrain、Elkem社製）、及びアセチレンブラック（ＡＢ）1g（商品名：デンカブラック、デンカ(株)製）を計りとり、自転公転泡攪拌機（商品名：泡とり練太郎、型式：ＡＲ－２５０、(株)シンキー製）を用いて回転速度2000rpmで１０分間混合した。次いで、バインダー溶液Ｋ－１を10g加え、自転公転泡攪拌機を用いて2000rpmで３時間混合した。次いでイオン交換水4ｇを加え、自転公転泡攪拌機を用いて2000rpmで１０分間混合した。次いで、自転公転泡攪拌機で５分間脱泡し、得られた混合物（固形分質量比でＳｉ：ＡＢ：バインダー溶液の固形分＝８０：１０：１０）をスラリー組成物とした。該スラリー組成物は、集電体上に塗布した後に乾燥させることにより、シリコンを８０ｗｔ％、ＡＢを１０ｗｔ％、バインダーを１０ｗｔ％含有する被膜となるものである。 Example 1 Production of a battery using the electrode of the present invention
(1) Production of slurry composition of the present invention 8 g of silicon powder (particle size: average particle size 2.4 μm, trade name: Silgrain, manufactured by Elkem) and 1 g of acetylene black (AB) (trade name: Denka Black, Denka) (Made by Co., Ltd.) was measured and mixed for 10 minutes at a rotational speed of 2000 rpm using a rotating and rotating foam stirrer (trade name: Netsutaro Awatori, model: AR-250, manufactured by Shinky Co., Ltd.). Next, 10 g of binder solution K-1 was added and mixed for 3 hours at 2000 rpm using a rotating and rotating bubble stirrer. Next, 4 g of ion-exchanged water was added and mixed for 10 minutes at 2000 rpm using a rotating and rotating bubble stirrer. Next, the mixture was defoamed for 5 minutes with a rotating and rotating foam stirrer, and the resulting mixture (solid content: Si: AB: solid content of binder solution = 80: 10: 10) was used as the slurry composition. The slurry composition is a film containing 80 wt% silicon, 10 wt% AB, and 10 wt% binder by drying after coating on the current collector.
（２）本発明のリチウム電池用電極の作製
　（１）で得られたスラリー組成物を、ドクターブレード（テスター産業(株)製）と塗工機（商品名：MINI-COATER MC-20、宝泉(株)製）を用いて、厚さ２０μｍの銅箔集電体上に活物質のＳｉ質量が3mg/cm2になるように塗布した。その後、空気中にて８０℃で乾燥し、次いで真空下にて１５０℃で１２時間乾燥した。集電体上の膜の厚さは、ノギスで測定し、約４０～２０μｍであった。得られた集電体をロールプレス機（商品名：HSR-60150、宝泉(株)製）でプレスし、シリコン活物質密度1.4mg/cm3のリチウム電池用電極を作製した。 (2) Preparation of electrode for lithium battery of the present invention (1) The slurry composition obtained in (1) was prepared using a doctor blade (manufactured by Tester Sangyo Co., Ltd.) and a coating machine (trade name: MINI-COATER MC-20, Takara (Made by Izumi Co., Ltd.) was applied on a 20 μm thick copper foil current collector so that the Si mass of the active material was 3 mg / cm 2 . Thereafter, it was dried at 80 ° C. in air, and then dried at 150 ° C. for 12 hours under vacuum. The thickness of the film on the current collector was about 40-20 μm as measured with calipers. The obtained current collector was pressed with a roll press (trade name: HSR-60150, manufactured by Hosen Co., Ltd.) to produce a lithium battery electrode having a silicon active material density of 1.4 mg / cm 3 .
（３）コイン型電池の製造
　（２）で得られた電極、リチウム箔電極、１ＭのＬｉＰＦ6を含む炭酸エチレン（ＥＣ）／炭酸ジメチル（ＤＭＣ）（体積比で１：１）溶液及びセパレータからなるコイン型電池を、アルゴンで満たしたグローブボックス中で組み立てた。 (3) Manufacture of coin-type battery From the electrode obtained in (2), lithium foil electrode, ethylene carbonate (EC) / dimethyl carbonate (DMC) (1: 1 by volume) solution and separator containing 1M LiPF 6 The coin cell battery was assembled in a glove box filled with argon.
実施例２～１４　本発明の電極を用いた電池の製造
　バインダー溶液Ｋ－１　10gの代わりに、バインダー溶液Ｋ－２～１４　10gをそれぞれ用いた以外は実施例１と同様の方法により、スラリー組成物、リチウム電池用電極及びコイン型電池を製造した。 Examples 2 to 14 Production of a battery using the electrode of the present invention A slurry composition was prepared in the same manner as in Example 1 except that 10 g of binder solution K-2 to 14 10 g was used instead of 10 g of binder solution K-1. Products, lithium battery electrodes and coin-type batteries.
比較例１，２　電池の製造
　バインダー溶液Ｋ－１　10gの代わりに、バインダー溶液Ｊ－１又はＪ－２　10gをそれぞれ用いた以外は実施例１と同様の方法により、スラリー組成物、リチウム電池用電極及びコイン型電池を製造した。 Comparative Examples 1 and 2 Production of Battery A slurry composition for lithium batteries was prepared in the same manner as in Example 1 except that 10 g of binder solution J-1 or J-2 was used instead of 10 g of binder solution K-1. Electrodes and coin-type batteries were manufactured.
比較例３　電池の製造
　バインダー溶液Ｋ－１　10gの代わりに、架橋ホモポリマー溶液Ｈ－２　10gを用いた以外は実施例１と同様の方法により、スラリー組成物、リチウム電池用電極及びコイン型電池を製造した。 Comparative Example 3 Production of Battery In the same manner as in Example 1 except that 10 g of the crosslinked homopolymer solution H-2 was used instead of 10 g of the binder solution K-1, a slurry composition, an electrode for a lithium battery, and a coin-type battery Manufactured.
実験例２　各種スラリー組成物を用いたスラリー分散性の測定
　ガラス製の目盛付き50mL遠沈管に実施例１～１４及び比較例１～３において作製したスラリー組成物5gを加え、さらにイオン交換水20mLを加えた。10分間振とう機で撹拌した後、６０分間静置し、遠沈管の背面に青い紙を設置した。遠沈管の目盛0～20mLの全ての範囲において背景の青色が見えない場合を○（分散性が良好）、0～15mLの範囲においては背景の青色が見えないが、15～20mLの範囲においては背景の青色が見える場合を△（沈降物が僅かにある）、5～20mLの範囲において背景の青色が見える場合を×（分散性が悪い）とした。
　得られた結果を表２に示す。 Experimental Example 2 Measurement of Slurry Dispersibility Using Various Slurry Compositions 5 g of the slurry compositions prepared in Examples 1 to 14 and Comparative Examples 1 to 3 were added to a glass-scaled 50 mL centrifuge tube and further 20 mL of ion-exchanged water. Was added. After stirring for 10 minutes with a shaker, the mixture was allowed to stand for 60 minutes, and blue paper was placed on the back of the centrifuge tube. When the background blue color is not visible in the entire range of the centrifuge tube scale 0 to 20 mL (good dispersibility), the background blue color is not visible in the 0 to 15 mL range, but in the 15 to 20 mL range The case where the blue color of the background is visible is indicated by Δ (there is a slight amount of sediment), and the case where the blue color of the background is visible in the range of 5 to 20 mL is indicated by x (poor dispersibility).
The obtained results are shown in Table 2.
実験例３　各種電極を用いた剥離強度の測定
　実施例１～１４及び比較例１～３において作製した電極を幅5mm・長さ約50mmの短冊状にカッターで切断し、電極端5mmを残すように、両面テープを貼ったガラス製スライドグラスに貼り付けた。残した電極端5mm部分にカプトンテープを貼り、該電極端とは反対側の端を、剥離角が９０度になるように剥離試験機（商品名：FGS-TV、型番：デジタルフォースゲージ FGP-0.5、日本電産シンポ(株)製）にセットし、10mm/分の速さで引き上げた。得られたデータの30mm分の平均値を剥離強度（単位：Ｎ）とした。
　得られた結果を表２に示す。
　尚、ここで得られたデータは、主に活物質層を銅箔から剥がす時に必要な力を表している。従って、剥離強度が強い場合は、スラリー組成物（ここではシリコン、ＡＢ及びバインダー）からなる活物質層が集電体の銅箔と強く結着していることを意味する。 Experimental Example 3 Measurement of peel strength using various electrodes The electrodes prepared in Examples 1 to 14 and Comparative Examples 1 to 3 were cut into strips having a width of 5 mm and a length of about 50 mm with a cutter, leaving an electrode end of 5 mm. And a glass slide glass with a double-sided tape. Apply Kapton tape to the remaining 5mm electrode end, and peel tester (trade name: FGS-TV, model number: Digital Force Gauge FGP-) so that the peel angle is 90 degrees on the end opposite to the electrode end. 0.5, manufactured by Nidec Sympo Co., Ltd.) and pulled up at a speed of 10 mm / min. The average value for 30 mm of the obtained data was defined as peel strength (unit: N).
The obtained results are shown in Table 2.
The data obtained here mainly represents the force required when the active material layer is peeled from the copper foil. Therefore, when the peel strength is strong, it means that the active material layer made of the slurry composition (here, silicon, AB and binder) is strongly bound to the copper foil of the current collector.
実験例４　各種電池を用いた充放電試験
　実施例１～１４及び比較例１～３において作製したコイン型電池を用いて、下記条件で定電流充放電試験を行った。
充放電の条件を下記に示す。
・対極：Ｌｉ箔
・電解液：１Ｍ　ＬｉＰＦ６　ＥＣ／ＤＭＣ混合溶液（体積比１：１）
・測定装置：ABE1024-5V 0.1A-4充放電試験装置（エレクトロフィールド社製）
・電位及び電流密度
　　電位範囲　２．０－０．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋)
　　電流密度　初回５０ｍＡ／ｇ、２回以降５０ｍＡ／ｇ
　各電池を用いて得られた初回充放電での負極の放電容量および５回目サイクル後の負極の放電容量の値から、下記式を用いて容量維持率（％）を算出した。
容量維持率（％）＝５回サイクル後の放電容量÷初回の放電容量×１００
　得られた結果を表２に示す。 Experimental Example 4 Charge / Discharge Test Using Various Batteries Using the coin-type batteries prepared in Examples 1 to 14 and Comparative Examples 1 to 3, a constant current charge / discharge test was performed under the following conditions.
The charge / discharge conditions are shown below.
-Counter electrode: Li foil-Electrolytic solution: 1M LiPF 6 EC / DMC mixed solution (volume ratio 1: 1)
・ Measuring device: ABE1024-5V 0.1A-4 charge / discharge tester (manufactured by Electrofield)
-Potential and current density Potential range 2.0-0.0 V (vs. Li / Li + )
Current density 50mA / g for the first time, 50mA / g for the second and subsequent times
From the value of the discharge capacity of the negative electrode at the first charge / discharge obtained using each battery and the value of the discharge capacity of the negative electrode after the fifth cycle, the capacity retention rate (%) was calculated using the following formula.
Capacity retention rate (%) = discharge capacity after 5 cycles / first discharge capacity × 100
The obtained results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000148
Figure JPOXMLDOC01-appb-T000148
　表２より、実施例１～１４の本発明のスラリー組成物はいずれもスラリー分散性が良好であったのに対し、比較例１～３のスラリー組成物はいずれもスラリー分散性が悪かった。活物質や導電助剤がスラリー中で均等に分散することは、電極を作製する上で重要な要素である。導電助剤であるＡＢがスラリー中で分散せずに凝集を起こした場合、電極内の導電パスが形成されず、電池性能は低下する。従って、実施例１～１４のスラリー組成物はそのスラリー分散性が良好であったため、これを用いて作製した電極は、電極内の導電パスが形成された結果、電池性能が向上したと考えられる。 From Table 2, all of the slurry compositions of the present invention of Examples 1 to 14 had good slurry dispersibility, while all of the slurry compositions of Comparative Examples 1 to 3 had poor slurry dispersibility. It is an important factor in producing an electrode that the active material and the conductive additive are evenly dispersed in the slurry. When AB, which is a conductive auxiliary agent, does not disperse in the slurry and agglomerates, a conductive path in the electrode is not formed, and battery performance deteriorates. Therefore, since the slurry compositions of Examples 1 to 14 had good slurry dispersibility, it was considered that the electrodes produced using the slurry compositions had improved battery performance as a result of the formation of conductive paths in the electrodes. .
　また、実施例１～１４の本発明の電極はいずれも、比較例１～３の電極よりも高い剥離強度を示すことが分かった。これは、本発明に係るアルコールが集電体との結着を向上させていることや、ホモポリマーとコポリマー又はホモポリマー同士が本発明に係るアルコールを介して結合することで電極に均等に配置され、集電体の銅や活物質同士の結着が高まったためと考えられる。 It was also found that all the electrodes of the present invention of Examples 1 to 14 showed higher peel strength than the electrodes of Comparative Examples 1 to 3. This is because the alcohol according to the present invention improves the binding with the current collector, and the homopolymer and the copolymer or the homopolymers are bonded to each other through the alcohol according to the present invention so that they are evenly arranged on the electrode. This is thought to be due to the increased binding between the copper and the active material of the current collector.
　さらに、本発明の電極を用いた実施例１～１４の電池はいずれも、比較例１～３の電池よりも高い容量維持率を示すことが分かった。これは、ホモポリマーとコポリマー又はホモポリマー同士が本発明に係るアルコールを介して結合することで、電極に均等に配置されて活物質表面を包み込んだ結果、ポリマーが不均一な状態のミクロ層分離のような不具合が無いことにより、活物質表面のほとんどが充放電に活用されたためと考えられる。 Furthermore, it was found that any of the batteries of Examples 1 to 14 using the electrode of the present invention showed a higher capacity retention rate than the batteries of Comparative Examples 1 to 3. This is because the homopolymer and the copolymer or the homopolymers are bonded via the alcohol according to the present invention, and are arranged evenly on the electrode and envelop the surface of the active material. This is probably because most of the active material surface was used for charging and discharging.
合成例２５　架橋ホモポリマーＡ－３の合成
　攪拌装置、冷却管、温度計、窒素導入管及び滴下装置を備えた200mLの丸底フラスコに、メチルエチルケトン（ＭＥＫ）20mL（和光純薬工業(株)製）を入れ、次いで、アクリル酸4g（56mmol、和光純薬工業(株)製）、ポリエチレングリコールジアクリレート0.014g（0.05mmol、新中村化学工業(株)製）及びジメチル2,2’-アゾビス(2-メチルプロピオネート)0.01g（0.04mmol、和光純薬工業(株)製）を加えて撹拌した。その後、窒素気流下、７０℃で４時間反応させた。反応中、ＭＥＫがわずかに揮発するため、必要に応じてＭＥＫを追加した。反応後、室温まで冷却し、白色固体を得た。得られた白色固体を真空乾燥して、架橋されたポリアクリル酸を得た。これを架橋ホモポリマーＡ－３とした。 Synthesis Example 25 Synthesis of Crosslinked Homopolymer A-3 A 200 mL round bottom flask equipped with a stirring device, a cooling tube, a thermometer, a nitrogen introduction tube and a dropping device was added to 20 mL of methyl ethyl ketone (MEK) (manufactured by Wako Pure Chemical Industries, Ltd.). ), And then acrylic acid 4 g (56 mmol, manufactured by Wako Pure Chemical Industries, Ltd.), polyethylene glycol diacrylate 0.014 g (0.05 mmol, manufactured by Shin-Nakamura Chemical Co., Ltd.) and dimethyl 2,2'-azobis ( 2-methylpropionate) 0.01 g (0.04 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred. Then, it was made to react at 70 degreeC under nitrogen stream for 4 hours. MEK was slightly volatilized during the reaction, so MEK was added as necessary. After the reaction, the mixture was cooled to room temperature to obtain a white solid. The obtained white solid was vacuum-dried to obtain a crosslinked polyacrylic acid. This was designated as crosslinked homopolymer A-3.
合成例２６　架橋ホモポリマーＡ－４の合成
　反応系中に、さらに1,4-ブタンジオール0.4g（和光純薬工業(株)製）を添加した以外は、合成例２５と同様の方法で重合反応に付し、架橋ホモポリマーＡ－４を得た。 Synthesis Example 26 Polymerization was carried out in the same manner as in Synthesis Example 25, except that 0.4 g of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the synthesis reaction system of crosslinked homopolymer A-4. The reaction was subjected to reaction to obtain a crosslinked homopolymer A-4.
合成例２７　架橋コポリマーＣ－３の合成
　アクリル酸4gの代わりに、アクリル酸2g（28mmol）及びアクリル酸-2-ヒドロキシエチル2g（17mmol、和光純薬工業(株)製）を用いた以外は、合成例２５と同様の方法で重合反応に付し、架橋コポリマーＣ－３を得た。 Synthesis Example 27 Synthesis of Crosslinked Copolymer C-3 Instead of 4 g of acrylic acid, 2 g (28 mmol) of acrylic acid and 2 g of 2-hydroxyethyl acrylate (17 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) were used. The polymer was subjected to a polymerization reaction in the same manner as in Synthesis Example 25 to obtain a crosslinked copolymer C-3.
合成例２８　架橋コポリマーＣ－４の合成
　反応系中に、さらに1,4-ブタンジオール0.4g（和光純薬工業(株)製）を添加した以外は、合成例２７と同様の方法で重合反応に付し、架橋コポリマーＣ－４を得た。 Synthesis Example 28 A polymerization reaction was performed in the same manner as in Synthesis Example 27, except that 0.4 g of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the synthesis reaction system of the crosslinked copolymer C-4. To give a crosslinked copolymer C-4.
合成例２９　架橋コポリマーＣ－５の合成
　反応系中に、さらにペンタエリスリトール0.4g（和光純薬工業(株)製）を添加した以外は、合成例２７と同様の方法で重合反応に付し、架橋コポリマーＣ－５を得た。 Synthesis Example 29 A polymerization reaction was performed in the same manner as in Synthesis Example 27, except that 0.4 g of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the synthesis reaction system of the crosslinked copolymer C-5 . Crosslinked copolymer C-5 was obtained.
実験例５　各種ポリマーの溶解性試験
　合成例２５～２９において得られた各種架橋ポリマー（架橋ホモポリマーＡ－３及びＡ－４、並びに架橋コポリマーＣ－３～Ｃ－５）について、下記（１）～（３）の溶解性試験を行った。溶媒に完全に溶解した場合を○、不溶であった場合を×とした。
　得られた結果を、各種架橋ポリマーのモノマー含有量及び２価～１０価のアルコール含有量と合わせて、表３に示す。
（１）水に対する溶解性試験
　各種架橋ポリマーの濃度が５％となる量のイオン交換水（Ｈ２Ｏ）を加え、室温にて溶解性試験を行った。
（２）水酸化ナトリウム水溶液に対する溶解性試験
　各種架橋ポリマーの中和度が８０％となる量の水酸化ナトリウム水溶液（ＮａＯＨ）（和光純薬工業(株)製）を加え、室温にて溶解性試験を行った。
（３）N-メチルピロリドンに対する溶解性試験
　各種架橋ポリマーの濃度が５％となる量のN-メチルピロリドン（ＮＭＰ）（和光純薬工業(株)製）を加え、室温にて溶解性試験を行った。 Experimental Example 5 Solubility test of various polymers Various cross-linked polymers (cross-linked homopolymers A-3 and A-4 and cross-linked copolymers C-3 to C-5) obtained in Synthesis Examples 25 to 29 are described in the following (1). The solubility test of (3) to (3) was conducted. The case where it was completely dissolved in the solvent was marked with ◯, and the case where it was insoluble was marked with ×.
The obtained results are shown in Table 3 together with the monomer content and divalent to 10-valent alcohol content of various crosslinked polymers.
(1) Solubility test in water Ion exchange water (H 2 O) was added in such an amount that the concentration of various cross-linked polymers was 5%, and a solubility test was performed at room temperature.
(2) Solubility test in aqueous sodium hydroxide solution Addition of sodium hydroxide aqueous solution (NaOH) (Wako Pure Chemical Industries, Ltd.) in an amount that the degree of neutralization of various cross-linked polymers is 80%, and solubility at room temperature. A test was conducted.
(3) Solubility test for N-methylpyrrolidone Addition of N-methylpyrrolidone (NMP) (made by Wako Pure Chemical Industries, Ltd.) in such an amount that the concentration of various cross-linked polymers is 5%, and conduct a solubility test at room temperature. went.
Figure JPOXMLDOC01-appb-T000149
Figure JPOXMLDOC01-appb-T000149
　表３より、２価～１０価のアルコール（1,4-ブタンジオール又はペンタエリスリトール）の共存下で重合反応を行ったポリマー（架橋ホモポリマーＡ－４、並びに架橋コポリマーＣ－４及びＣ－５）は、水、水酸化ナトリウム水溶液及びN-メチルピロリドンのいずれの溶媒にも溶解しないことが分かった。すなわち、（Ａ）ポリアクリル酸を含む１種以上のポリマーの製造において、（Ｂ）２価～１０価のアルコールを加えて重合反応を行った場合（言い換えれば、該ポリマーの重合反応と２価～１０価のアルコールによる結合反応を同時に行った場合）、得られたポリマーは水を始めとする種々の溶媒に溶解しないため、該ポリマーを電極作製に用いることが出来ないことが分かった。
　従って、本発明の結着剤組成物は、重合反応、並びに、要すれば中和処理及び／又は架橋反応を行い、所望の（Ａ）ポリアクリル酸を含む１種以上のポリマーを製造した上で、該ポリマーを（Ｂ）２価～１０価のアルコール及び（Ｃ）水と混合し、製造する必要があることが分かった。 From Table 3, polymers (crosslinked homopolymer A-4 and crosslinked copolymers C-4 and C-5) subjected to a polymerization reaction in the presence of divalent to 10-valent alcohol (1,4-butanediol or pentaerythritol) were used. ) Was not dissolved in any solvent of water, aqueous sodium hydroxide and N-methylpyrrolidone. That is, (A) in the production of one or more polymers containing polyacrylic acid, (B) when a polymerization reaction is carried out by adding a divalent to 10-valent alcohol (in other words, the polymerization reaction of the polymer and the divalent polymer It was found that the obtained polymer cannot be used for electrode preparation because the obtained polymer is not dissolved in various solvents such as water.
Therefore, the binder composition of the present invention is subjected to a polymerization reaction and, if necessary, a neutralization treatment and / or a crosslinking reaction to produce one or more kinds of polymers containing the desired (A) polyacrylic acid. It was found that it was necessary to prepare the polymer by mixing (B) a divalent to 10-valent alcohol and (C) water.

Claims (13)

  1. （Ａ）ポリアクリル酸を含む１種以上のポリマー、（Ｂ）２価～１０価のアルコール、及び（Ｃ）水を含んでなる結着剤組成物。 A binder composition comprising (A) one or more polymers containing polyacrylic acid, (B) a divalent to 10-valent alcohol, and (C) water.
  2. （Ｂ）の２価～１０価のアルコールが、下記一般式（Ｂ１）で示される化合物である、請求項１記載の組成物；
    Figure JPOXMLDOC01-appb-I000001
    （式中、Ｒ71は、炭素数１～６のアルキレン基を表し、Ｒ72は、ヒドロキシ基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ73は、水素原子、炭素数１～６のアルキル基又は炭素数１～６のヒドロキシアルキル基を表し、Ｒ74は、－Ｏ－を鎖中に有していてもよい炭素数１～６のアルキレン基を表し、ｒは０～４の整数を表す。ただし、複数のＲ72、複数のＲ73及び複数のＲ74は、それぞれ同一であっても異なっていてもよい。）     The composition according to claim 1, wherein the divalent to 10-valent alcohol of (B) is a compound represented by the following general formula (B1);
    Figure JPOXMLDOC01-appb-I000001
    Wherein R 71 represents an alkylene group having 1 to 6 carbon atoms, R 72 represents a hydroxy group or a hydroxyalkyl group having 1 to 6 carbon atoms, R 73 represents a hydrogen atom, 1 to 6 carbon atoms Or an alkyl group having 1 to 6 carbon atoms, R 74 represents an alkylene group having 1 to 6 carbon atoms which may have —O— in the chain, and r represents 0 to 4 carbon atoms. Represents an integer, provided that the plurality of R 72 , the plurality of R 73 and the plurality of R 74 may be the same or different.
  3. （Ａ）が、ポリアクリル酸、及び、アクリル酸由来のモノマー単位と、下記一般式（I）又は一般式（II）で示される化合物由来のモノマー単位１～２種とを構成成分とするコポリマーである、請求項１記載の組成物；
    Figure JPOXMLDOC01-appb-I000002
    ［式中、Ｒ1は、水素原子又はメチル基を表し（但し、Ｒ2が水素原子の場合、Ｒ1はメチル基を表す）、Ｒ2は、水素原子；炭素数１～２０のアルキル基；フッ素原子又はヒドロキシ基で置換された炭素数１～２０のアルキル基；炭素数６～１０のアリール基；炭素数７～１３のアリールアルキル基；炭素数２～９のアルコキシアルキル基；炭素数３～９のアルコキシアルコキシアルキル基；炭素数７～１３のアリールオキシアルキル基；炭素数５～７のモルホリノアルキル基；炭素数３～９のトリアルキルシリル基；酸素原子を有する又は酸素原子を有さない炭素数６～１２の脂環式炭化水素基；炭素数３～９のジアルキルアミノアルキル基；炭素数９～１４のヘキサヒドロフタルイミド－Ｎ－アルキル基；下記一般式（IV）で示される基
    Figure JPOXMLDOC01-appb-I000003
    （式中、Ｒ3は、ヒドロキシ基を置換基として有する又は無置換の炭素数１～６のアルキレン基を表し、Ｒ4は、水素原子、炭素数１～６のアルキル基、又はフェニル基を表し、ｖは２～２０の整数を表す。）；或いは、下記一般式（V）で示される基
    Figure JPOXMLDOC01-appb-I000004
    （式中、Ｒ5～Ｒ7は、それぞれ独立して炭素数１～３のアルキル基を表し、Ｒ8は、炭素数１～３のアルキレン基を表す。）を表す。］、
    Figure JPOXMLDOC01-appb-I000005
    （式中、Ｒ11は、水素原子又はメチル基を表し、Ｒ12は、水素原子又は炭素数１～６のアルキル基を表し、Ｒ13は、水素原子、炭素数１～６のアルキル基、炭素数３～９のジアルキルアミノアルキル基、又は炭素数１～６のヒドロキシアルキル基を表す。）。     (A) is a copolymer comprising polyacrylic acid and a monomer unit derived from acrylic acid and one or two monomer units derived from a compound represented by the following general formula (I) or general formula (II) The composition of claim 1, wherein
    Figure JPOXMLDOC01-appb-I000002
    [Wherein R 1 represents a hydrogen atom or a methyl group (provided that when R 2 is a hydrogen atom, R 1 represents a methyl group), R 2 represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or a hydroxy group; an aryl group having 6 to 10 carbon atoms; an arylalkyl group having 7 to 13 carbon atoms; an alkoxyalkyl group having 2 to 9 carbon atoms; An alkoxyalkoxyalkyl group having 3 to 9 carbon atoms; an aryloxyalkyl group having 7 to 13 carbon atoms; a morpholinoalkyl group having 5 to 7 carbon atoms; a trialkylsilyl group having 3 to 9 carbon atoms; having an oxygen atom or having an oxygen atom An alicyclic hydrocarbon group having 6 to 12 carbon atoms; a dialkylaminoalkyl group having 3 to 9 carbon atoms; a hexahydrophthalimide-N-alkyl group having 9 to 14 carbon atoms; represented by the following general formula (IV) Base
    Figure JPOXMLDOC01-appb-I000003
    (Wherein R 3 represents a hydroxyl group as a substituent or an unsubstituted alkylene group having 1 to 6 carbon atoms, and R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. V represents an integer of 2 to 20); or a group represented by the following general formula (V)
    Figure JPOXMLDOC01-appb-I000004
    (Wherein R 5 to R 7 each independently represents an alkyl group having 1 to 3 carbon atoms, and R 8 represents an alkylene group having 1 to 3 carbon atoms). ],
    Figure JPOXMLDOC01-appb-I000005
    (Wherein R 11 represents a hydrogen atom or a methyl group, R 12 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents a dialkylaminoalkyl group having 3 to 9 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.)
  4. ポリアクリル酸が、下記一般式［１］～［１３］記載の化合物及び下記一般式［１４］記載のポリマーから選ばれる架橋剤により架橋されたものである、請求項１記載の組成物；
    Figure JPOXMLDOC01-appb-I000006
    （式中、ａは１～６の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000007
    ［式中、Ｒ25及びＲ26は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ21は、炭素数１～２０のアルキレン基、下記一般式［２－１］で示される基
    Figure JPOXMLDOC01-appb-I000008
    （式中、Ｒ22は、炭素数１～６のアルキレン基を表し、ｂは１～６の整数を表す。）、又は下記一般式［２－２］で示される基
    Figure JPOXMLDOC01-appb-I000009
    （式中、Ｒ23及びＲ24は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｃは１～２２の整数を表す。）を表す。］、
    Figure JPOXMLDOC01-appb-I000010
    （式中、Ｒ27～Ｒ33は、それぞれ独立して、炭素数１～３のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000011
    （式中、Ｒ34～Ｒ37は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｄは１～６の整数を表し、ｅは０～６の整数を表し、ｆ及びｇはそれぞれ独立して０又は１の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000012
    （式中、Ｒ38～Ｒ45は、それぞれ独立して、水素原子、ビニル基又はビニルケトン基を表し、これらの少なくとも２つ以上はビニル基又はビニルケトン基である。）、
    Figure JPOXMLDOC01-appb-I000013
    （式中、Ｒ46～Ｒ48は、それぞれ独立して、炭素数１～６のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000014
    （式中、環Ar1は、ベンゼン環又はナフタレン環を表し、Ｒ49は、炭素数１～６のアルキレン基を表し、ｈは２～４の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000015
    （式中、環Ar2及び環Ar3は、それぞれ独立して、ベンゼン環又はナフタレン環を表し、Ｒ50は、炭素数１～６のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000016
    （式中、環Ar4は、ベンゼン環又はナフタレン環を表す。）、
    Figure JPOXMLDOC01-appb-I000017
    （式中、ｉは０～６の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000018
    （式中、Ｒ51は、炭素数１～６のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000019
    ［式中、Ｒ52は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１２－１］で示される基
    Figure JPOXMLDOC01-appb-I000020
    （式中、Ｒ53は、炭素数１～６のアルキル基を表し、Ｒ54は、炭素数１～６のアルキレン基を表し、環Ar5は、ベンゼン環又はナフタレン環を表し、ｊは、０～４の整数を表す。）、或いは、下記一般式［１２－２］で示される基
    Figure JPOXMLDOC01-appb-I000021
    （式中、Ｒ55は、炭素数１～６のアルキレン基を表し、Ｒ53、Ｒ54、環Ar5及びｊは、上記と同じ。）を表す。］、
    Figure JPOXMLDOC01-appb-I000022
    ［式中、Ｒ56及びＲ57は、それぞれ独立して、置換基を有する又は無置換の炭素数１～６のアルキル基、置換基を有する又は無置換の炭素数６～１０のアリール基、或いは、下記一般式［１３－１］で示される基
    Figure JPOXMLDOC01-appb-I000023
    （式中、Ｒ58は、炭素数１～６のアルキル基を表し、Ｒ59は、炭素数１～６のアルキレン基を表し、環Ar6は、ベンゼン環又はナフタレン環を表し、ｋは、０～５の整数を表す。）を表す。］、
    Figure JPOXMLDOC01-appb-I000024
    ［式中、Ｒ60は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１４－１］又は［１４－２］で示される基
    Figure JPOXMLDOC01-appb-I000025
    （式中、Ｒ61は、炭素数１～６のアルキル基を表し、Ｒ62は、炭素数１～６のアルキレン基を表し、環Ar7は、ベンゼン環又はナフタレン環を表し、ｐは、０～４の整数を表す。）、或いは、下記一般式［１４－３］で示される基
    Figure JPOXMLDOC01-appb-I000026
    （式中、Ｒ63は、炭素数１～６のアルキレン基を表し、Ｒ61、Ｒ62、環Ar7及びｐは、上記と同じ。）を表し、ｍは１０～１００００の整数を表す。］。     The composition according to claim 1, wherein the polyacrylic acid is crosslinked with a crosslinking agent selected from the compounds represented by the following general formulas [1] to [13] and the polymer represented by the following general formula [14];
    Figure JPOXMLDOC01-appb-I000006
    (Wherein, a represents an integer of 1 to 6),
    Figure JPOXMLDOC01-appb-I000007
    [Wherein R 25 and R 26 each independently represent a hydrogen atom or a methyl group, R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1]
    Figure JPOXMLDOC01-appb-I000008
    (Wherein R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6), or a group represented by the following general formula [2-2]
    Figure JPOXMLDOC01-appb-I000009
    (Wherein R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22). ],
    Figure JPOXMLDOC01-appb-I000010
    (Wherein R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms),
    Figure JPOXMLDOC01-appb-I000011
    (Wherein R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms, d represents an integer of 1 to 6, e represents an integer of 0 to 6, f and g Each independently represents an integer of 0 or 1.)
    Figure JPOXMLDOC01-appb-I000012
    (Wherein R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group).
    Figure JPOXMLDOC01-appb-I000013
    (Wherein R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms),
    Figure JPOXMLDOC01-appb-I000014
    (In the formula, ring Ar 1 represents a benzene ring or a naphthalene ring, R 49 represents an alkylene group having 1 to 6 carbon atoms, and h represents an integer of 2 to 4).
    Figure JPOXMLDOC01-appb-I000015
    (In the formula, each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring, and R 50 represents an alkylene group having 1 to 6 carbon atoms).
    Figure JPOXMLDOC01-appb-I000016
    (Wherein the ring Ar 4 represents a benzene ring or a naphthalene ring),
    Figure JPOXMLDOC01-appb-I000017
    (Wherein i represents an integer of 0 to 6),
    Figure JPOXMLDOC01-appb-I000018
    (Wherein R 51 represents an alkylene group having 1 to 6 carbon atoms),
    Figure JPOXMLDOC01-appb-I000019
    [Wherein R 52 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [12-1] Group represented by
    Figure JPOXMLDOC01-appb-I000020
    (Wherein R 53 represents an alkyl group having 1 to 6 carbon atoms, R 54 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 5 represents a benzene ring or a naphthalene ring, j is Represents an integer of 0 to 4, or a group represented by the following general formula [12-2]
    Figure JPOXMLDOC01-appb-I000021
    (Wherein R 55 represents an alkylene group having 1 to 6 carbon atoms, and R 53 , R 54 , and rings Ar 5 and j are the same as above). ],
    Figure JPOXMLDOC01-appb-I000022
    [Wherein, R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1]
    Figure JPOXMLDOC01-appb-I000023
    (Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5). ],
    Figure JPOXMLDOC01-appb-I000024
    [Wherein R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2]
    Figure JPOXMLDOC01-appb-I000025
    (Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3]
    Figure JPOXMLDOC01-appb-I000026
    (Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000. ].
  5. ポリアクリル酸及び／又はコポリマーが、下記一般式［１］～［１３］記載の化合物及び下記一般式［１４］記載のポリマーから選ばれる架橋剤により架橋されたものである、請求項３記載の組成物；
    Figure JPOXMLDOC01-appb-I000027
    （式中、ａは１～６の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000028
    ［式中、Ｒ25及びＲ26は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ21は、炭素数１～２０のアルキレン基、下記一般式［２－１］で示される基
    Figure JPOXMLDOC01-appb-I000029
    （式中、Ｒ22は、炭素数１～６のアルキレン基を表し、ｂは１～６の整数を表す。）、又は下記一般式［２－２］で示される基
    Figure JPOXMLDOC01-appb-I000030
    （式中、Ｒ23及びＲ24は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｃは１～２２の整数を表す。）を表す。］、
    Figure JPOXMLDOC01-appb-I000031
    （式中、Ｒ27～Ｒ33は、それぞれ独立して、炭素数１～３のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000032
    （式中、Ｒ34～Ｒ37は、それぞれ独立して、炭素数１～６のアルキレン基を表し、ｄは１～６の整数を表し、ｅは０～６の整数を表し、ｆ及びｇはそれぞれ独立して０又は１の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000033
    （式中、Ｒ38～Ｒ45は、それぞれ独立して、水素原子、ビニル基又はビニルケトン基を表し、これらの少なくとも２つ以上はビニル基又はビニルケトン基である。）、
    Figure JPOXMLDOC01-appb-I000034
    （式中、Ｒ46～Ｒ48は、それぞれ独立して、炭素数１～６のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000035
    （式中、環Ar1は、ベンゼン環又はナフタレン環を表し、Ｒ49は、炭素数１～６のアルキレン基を表し、ｈは２～４の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000036
    （式中、環Ar2及び環Ar3は、それぞれ独立して、ベンゼン環又はナフタレン環を表し、Ｒ50は、炭素数１～６のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000037
    （式中、環Ar4は、ベンゼン環又はナフタレン環を表す。）、
    Figure JPOXMLDOC01-appb-I000038
    （式中、ｉは０～６の整数を表す。）、
    Figure JPOXMLDOC01-appb-I000039
    （式中、Ｒ51は、炭素数１～６のアルキレン基を表す。）、
    Figure JPOXMLDOC01-appb-I000040
    ［式中、Ｒ52は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１２－１］で示される基
    Figure JPOXMLDOC01-appb-I000041
    （式中、Ｒ53は、炭素数１～６のアルキル基を表し、Ｒ54は、炭素数１～６のアルキレン基を表し、環Ar5は、ベンゼン環又はナフタレン環を表し、ｊは、０～４の整数を表す。）、或いは、下記一般式［１２－２］で示される基
    Figure JPOXMLDOC01-appb-I000042
    （式中、Ｒ55は、炭素数１～６のアルキレン基を表し、Ｒ53、Ｒ54、環Ar5及びｊは、上記と同じ。）を表す。］、
    Figure JPOXMLDOC01-appb-I000043
    ［式中、Ｒ56及びＲ57は、それぞれ独立して、置換基を有する又は無置換の炭素数１～６のアルキル基、置換基を有する又は無置換の炭素数６～１０のアリール基、或いは、下記一般式［１３－１］で示される基
    Figure JPOXMLDOC01-appb-I000044
    （式中、Ｒ58は、炭素数１～６のアルキル基を表し、Ｒ59は、炭素数１～６のアルキレン基を表し、環Ar6は、ベンゼン環又はナフタレン環を表し、ｋは、０～５の整数を表す。）を表す。］、
    Figure JPOXMLDOC01-appb-I000045
    ［式中、Ｒ60は、置換基を有する又は無置換の炭素数１～６のアルキレン基、置換基を有する又は無置換の炭素数６～１０のアリーレン基、下記一般式［１４－１］又は［１４－２］で示される基
    Figure JPOXMLDOC01-appb-I000046
    （式中、Ｒ61は、炭素数１～６のアルキル基を表し、Ｒ62は、炭素数１～６のアルキレン基を表し、環Ar7は、ベンゼン環又はナフタレン環を表し、ｐは、０～４の整数を表す。）、或いは、下記一般式［１４－３］で示される基
    Figure JPOXMLDOC01-appb-I000047
    （式中、Ｒ63は、炭素数１～６のアルキレン基を表し、Ｒ61、Ｒ62、環Ar7及びｐは、上記と同じ。）を表し、ｍは１０～１００００の整数を表す。］。     The polyacrylic acid and / or copolymer is crosslinked by a crosslinking agent selected from compounds represented by the following general formulas [1] to [13] and polymers represented by the following general formula [14]. Composition;
    Figure JPOXMLDOC01-appb-I000027
    (Wherein, a represents an integer of 1 to 6),
    Figure JPOXMLDOC01-appb-I000028
    [Wherein R 25 and R 26 each independently represent a hydrogen atom or a methyl group, R 21 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1]
    Figure JPOXMLDOC01-appb-I000029
    (Wherein R 22 represents an alkylene group having 1 to 6 carbon atoms, and b represents an integer of 1 to 6), or a group represented by the following general formula [2-2]
    Figure JPOXMLDOC01-appb-I000030
    (Wherein R 23 and R 24 each independently represents an alkylene group having 1 to 6 carbon atoms, and c represents an integer of 1 to 22). ],
    Figure JPOXMLDOC01-appb-I000031
    (Wherein R 27 to R 33 each independently represents an alkylene group having 1 to 3 carbon atoms),
    Figure JPOXMLDOC01-appb-I000032
    (Wherein R 34 to R 37 each independently represents an alkylene group having 1 to 6 carbon atoms, d represents an integer of 1 to 6, e represents an integer of 0 to 6, f and g Each independently represents an integer of 0 or 1.)
    Figure JPOXMLDOC01-appb-I000033
    (Wherein R 38 to R 45 each independently represents a hydrogen atom, a vinyl group or a vinyl ketone group, and at least two of these are a vinyl group or a vinyl ketone group).
    Figure JPOXMLDOC01-appb-I000034
    (Wherein R 46 to R 48 each independently represents an alkylene group having 1 to 6 carbon atoms),
    Figure JPOXMLDOC01-appb-I000035
    (In the formula, ring Ar 1 represents a benzene ring or a naphthalene ring, R 49 represents an alkylene group having 1 to 6 carbon atoms, and h represents an integer of 2 to 4).
    Figure JPOXMLDOC01-appb-I000036
    (In the formula, each of the ring Ar 2 and the ring Ar 3 independently represents a benzene ring or a naphthalene ring, and R 50 represents an alkylene group having 1 to 6 carbon atoms).
    Figure JPOXMLDOC01-appb-I000037
    (Wherein the ring Ar 4 represents a benzene ring or a naphthalene ring),
    Figure JPOXMLDOC01-appb-I000038
    (Wherein i represents an integer of 0 to 6),
    Figure JPOXMLDOC01-appb-I000039
    (Wherein R 51 represents an alkylene group having 1 to 6 carbon atoms),
    Figure JPOXMLDOC01-appb-I000040
    [Wherein R 52 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [12-1] Group represented by
    Figure JPOXMLDOC01-appb-I000041
    (Wherein R 53 represents an alkyl group having 1 to 6 carbon atoms, R 54 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 5 represents a benzene ring or a naphthalene ring, j is Represents an integer of 0 to 4, or a group represented by the following general formula [12-2]
    Figure JPOXMLDOC01-appb-I000042
    (Wherein R 55 represents an alkylene group having 1 to 6 carbon atoms, and R 53 , R 54 , and rings Ar 5 and j are the same as above). ],
    Figure JPOXMLDOC01-appb-I000043
    [Wherein, R 56 and R 57 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Alternatively, a group represented by the following general formula [13-1]
    Figure JPOXMLDOC01-appb-I000044
    (Wherein R 58 represents an alkyl group having 1 to 6 carbon atoms, R 59 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 6 represents a benzene ring or a naphthalene ring, and k is Represents an integer of 0 to 5). ],
    Figure JPOXMLDOC01-appb-I000045
    [Wherein R 60 represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or the following general formula [14-1] Or a group represented by [14-2]
    Figure JPOXMLDOC01-appb-I000046
    (Wherein R 61 represents an alkyl group having 1 to 6 carbon atoms, R 62 represents an alkylene group having 1 to 6 carbon atoms, ring Ar 7 represents a benzene ring or a naphthalene ring, and p is Represents an integer of 0 to 4, or a group represented by the following general formula [14-3]
    Figure JPOXMLDOC01-appb-I000047
    (Wherein R 63 represents an alkylene group having 1 to 6 carbon atoms, and R 61 , R 62 , and rings Ar 7 and p are the same as above), and m represents an integer of 10 to 10,000. ].
  6. ポリアクリル酸及びコポリマーが、一般式［１］～［１３］記載の化合物及び一般式［１４］記載のポリマーから選ばれる架橋剤により架橋されたものである、請求項５記載の組成物。 The composition according to claim 5, wherein the polyacrylic acid and the copolymer are crosslinked with a crosslinking agent selected from the compounds represented by the general formulas [1] to [13] and the polymer represented by the general formula [14].
  7. １）シリコンを含有する活物質、２）導電助剤、及び３）請求項１記載の結着剤組成物を含んでなるリチウム電池用のスラリー組成物。 A slurry composition for a lithium battery, comprising 1) an active material containing silicon, 2) a conductive additive, and 3) a binder composition according to claim 1.
  8. シリコンを含有する活物質が、シリコン；シリコン酸化物；金属と結合したシリコン；或いは、炭素、シリコン、シリコン酸化物又は金属と結合したシリコンのうち少なくとも２種以上を混合したものを含有する、請求項７記載の組成物。 The active material containing silicon contains silicon, silicon oxide, silicon bonded to metal, or a mixture of at least two of carbon, silicon, silicon oxide, or silicon bonded to metal. Item 8. The composition according to Item 7.
  9. 負極作製用である、請求項７記載の組成物。 The composition according to claim 7, which is for producing a negative electrode.
  10. １）シリコンを含有する活物質、２）導電助剤、３）請求項１記載の結着剤組成物由来の結着剤、及び４）集電体を有するリチウム電池用の電極。 An electrode for a lithium battery having 1) an active material containing silicon, 2) a conductive additive, 3) a binder derived from the binder composition according to claim 1, and 4) a current collector.
  11. シリコンを含有する活物質が、シリコン；シリコン酸化物；金属と結合したシリコン；或いは、炭素、シリコン、シリコン酸化物又は金属と結合したシリコンのうち少なくとも２種以上を混合したものを含有する、請求項１０記載の電極。 The active material containing silicon contains silicon, silicon oxide, silicon bonded to metal, or a mixture of at least two of carbon, silicon, silicon oxide, or silicon bonded to metal. Item 10. The electrode according to Item 10.
  12. 電極が負極である、請求項１０記載の電極。 The electrode according to claim 10, wherein the electrode is a negative electrode.
  13. 請求項７記載のスラリー組成物を集電体上に塗布した後、乾燥させることを特徴とする、リチウム電池用の電極作製方法。 A method for producing an electrode for a lithium battery, wherein the slurry composition according to claim 7 is applied on a current collector and then dried.
PCT/JP2018/003513 2017-02-03 2018-02-02 Binder agent composition for lithium battery WO2018143382A1 (en)

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EP18747843.3A EP3579313B1 (en) 2017-02-03 2018-02-02 Use of a binder agent composition for lithium battery, slurry composition for lithium batteries comprising the binder composition, and electrode using the binder composition
KR1020197014353A KR102548023B1 (en) 2017-02-03 2018-02-02 Binder composition for lithium battery
CN201880004294.1A CN109923711B (en) 2017-02-03 2018-02-02 Binder composition for lithium battery
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